Articles from Plasticized Polyolefin Compositions

ABSTRACT

The present invention relates to articles made from plasticized polyolefin compositions comprising a polyolefin and a non-functionalized hydrocarbon plasticizer.

PRIORITY CLAIM

This application is a continuation in part of U.S. Ser. No. 640,435,filed Aug. 12, 2003 which claims priority from U.S. Ser. No. 60/402,665filed on Aug. 12, 2002 and this application is a continuation in part ofU.S. Ser. No. 10/634,351 filed Aug. 4, 2003 which claims priority fromU.S. Ser. No. 60/402,665 filed on Aug. 12, 2002.

FIELD OF THE INVENTION

The present invention relates articles produced from plasticizedpolyolefins comprising a polyolefin and a non-functionalizedplasticizer.

BACKGROUND OF THE INVENTION

Polyolefins are useful in any number of everyday articles. However, onedrawback to many polyolefins, especially propylene homopolymers and somepropylene copolymers, is their relatively high glass transitiontemperature. This characteristic makes these polyolefins brittle,especially at low temperatures. Many applications of polyolefins benefitfrom having useful properties over a broad range of temperatures;consequently, there is a need to provide polyolefins that can maintaindesirable characteristics such as high or low temperature performance,etc., while maintaining or improving upon the impact strength andtoughness at lower temperatures. In particular, it would be advantageousto provide a propylene polymer possessing improved toughness and or highuse temperature without sacrificing its other desirable properties.

Addition of a plasticizer or other substance to a polyolefin is one wayto improve such properties as impact strength and toughness. Some patentdisclosures directed to such an end are U.S. Pat. No. 4,960,820; U.S.Pat. No. 4,132,698; U.S. Pat. No. 3,201,364; WO 02/31044; WO 01/18109A1; and EP 0 300 689 A2. These disclosures are directed to polyolefinsand elastomers blended with functionalized plasticizers. Thefunctionalized plasticizers are materials such as mineral oils whichcontain aromatic groups, and high (greater than −20° C.) pour pointcompounds. Use of these compounds typically does not preserve thetransparency of the polyolefin, and impact strength is often notimproved.

WO 98/44041 discloses plastic based sheet like material for a structure,especially a floor covering, which contains in a blend a plastic matrixcomprising a chlorine free polyolefin or mixture of polyolefins and aplasticizer characterized in that the plasticizer is an oligomericpolyalphaolefin type substance.

Other background references include EP 0 448 259 A, EP 1 028 145 A, U.S.Pat. Nos. 4,073,782, and 3,415,925.

What is needed is a polyolefin with lower flexural modulus, lower glasstransition temperature, and higher impact strength near and below 0° C.,while not materially influencing the peak melting temperature of thepolyolefin, the polyolefin crystallization rate, or its clarity, andwith minimal migration of plasticizer to the surface of fabricatedarticles. A plasticized polyolefin according to this invention canfulfill these needs. More specifically, there is a need for aplasticized polypropylene that can be used in such applications as foodcontainers, health care products, durable household and office goods,squeeze bottles, clear flexible film and sheet, automotive interior trimand facia, wire, cable, pipe, and toys.

Likewise, a plasticized polyolefin with improved softness, betterflexibility (especially lower flexural modulus), a depressed glasstransition temperature, and or improved impact strength especially atlow temperatures (below 0° C.), where at the same time the meltingtemperature of the polyolefin, the polyolefin crystallization rate, orits optical properties (especially clarity and haze) are not influenced,and with minimal migration of the plasticizer to the surface of articlesmade therefrom, is desirable.

It would be particularly desirable to plasticize polyolefins by using asimple, non-reactive compound such as a paraffin. However, it has beentaught that aliphatic or paraffinic compounds would impair theproperties of polyolefins, and was thus not recommended. (See, e.g.,CHEMICAL ADDITIVES FOR PLASTICS INDUSTRY 107-116 (Radian Corp., NoyesData Corporation, NJ 1987); WO 01/18109 A1).

Mineral oils, which have been used as extenders, softeners, and the likein various applications, consist of thousands of different compounds,many of which are undesirable in a lubricating system. Under moderate tohigh temperatures these compounds can volatilize and oxidize, even withthe addition of oxidation inhibitors.

Certain mineral oils, distinguished by their viscosity indices and theamount of saturates and sulfur they contain, have been classified asHydrocarbon Basestock Group I, II or III by the American PetroleumInstitute (API). Group I basestocks are solvent refined mineral oils.They contain the most unsaturates and sulfur and have the lowestviscosity indices. They define the bottom tier of lubricant performance.Group I basestocks are the least expensive to produce, and theycurrently account for abut 75 percent of all basestocks. These comprisethe bulk of the “conventional” basestocks. Groups II and III are theHigh Viscosity Index and Very High Viscosity Index basestocks. They arehydroprocessed mineral oils. The Group III oils contain less unsaturatesand sulfur than the Group I oils and have higher viscosity indices thanthe Group II oils do. Additional basestocks, named Groups IV and V, arealso used in the basestock industry. Rudnick and Shubkin (SyntheticLubricants and High-Performance Functional Fluids, Second edition,Rudnick, Shubkin, eds., Marcel Dekker, Inc. New York, 1999) describe thefive basestock Groups as typically being:

-   Group I—mineral oils refined using solvent extraction of aromatics,    solvent dewaxing, hydrofining to reduce sulfur content to produce    mineral oils with sulfur levels greater than 0.03 weight %,    saturates levels of 60 to 80 % and a viscosity index of about 90;-   Group II—mildly hydrocracked mineral oils with conventional solvent    extraction of aromatics, solvent dewaxing, and more severe    hydrofining to reduce sulfur levels to less than or equal to 0.03    weight % as well as removing double bonds from some of the olefinic    and aromatic compounds, saturate levels are greater than 95-98% and    VI is about 80-120;-   Group III—severely hydrotreated mineral oils with saturates levels    of some oils virtually 100%, sulfur contents are less than or equal    to 0.03 weight % (preferably between 0.001 and 0.01%) and VI is in    excess of 120;-   Group IV—poly(alpha-olefin)s-hydrocarbons manufactured by the    catalytic oligomerization of linear olefins having 6 or more carbon    atoms. In industry however, the Group IV basestocks are referred to    as “polyalphaolefins” and are generally thought of as a class of    synthetic basestock fluids produced by oligomerizing C₄ and greater    alphaolefins; and-   Group V—esters, polyethers, polyalkylene glycols, and includes all    other basestocks not included in Groups I, II, III and IV.

Other references of interest include: U.S. Pat. No. 5,869,555, U.S. Pat.No. 4,210,570, U.S. Pat. No. 4,110,185, GB 1,329,915, U.S. Pat. No.3,201,364, U.S. Pat. No. 4,774,277, JP01282280, FR2094870, JP69029554,Rubber Technology Handbook, Werner Hoffman, Hanser Publishers, New York,1989, pg 294-305, Additives for Plastics, J. Stepek, H. Daoust, SpringerVerlag, New York, 1983, pg-6-69.

U.S. Pat. No. 4,536,537 discloses blends of LLDPE (UC 7047),polypropylene (5520) and Synfluid 2CS, 4CS, or 6CS having a kinematicviscosity of 4.0 to 6.5 cSt at 100° F./38° C., however the Synfluid 4CSand 8CS are reported to “not work” (col 3, ln 12).

SUMMARY OF THE INVENTION

This invention relates to articles comprising plasticized polyolefincompositions comprising one or more polyolefins and one or morenon-functionalized plasticizers (“NFP”).

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graphical representation of the Storage Modulus (E′) as afunction of temperature for various plasticized propylene homopolymerexamples cited herein;

FIG. 2 is a graphical representation of the Tan δ as a function oftemperature for various plasticized propylene homopolymer examples citedherein;

FIG. 3 is a graphical representation of the Tan δ as a function oftemperature for various plasticized propylene copolymer examples citedherein;

FIG. 4 is a graphical representation of the Tan δ as a function oftemperature for various plasticized propylene impact copolymer examplescited herein;

FIG. 5 is a graphical representation of the melting heat flow from DSCas a function of temperature for various plasticized propylenehomopolymer samples illustrative of the invention;

FIG. 6 is a graphical representation of the crystallization heat flowfrom DSC as a function of temperature for various samples plasticizedpropylene homopolymer samples illustrative of the invention;

FIG. 7 is a graphical representation of the melting heat flow from DSCas a function of temperature for various plasticized propylene copolymersamples illustrative of the invention;

FIG. 8 is a graphical representation of the crystallization heat flowfrom DSC as a function of temperature for various plasticized propylenecopolymer samples illustrative of the invention;

FIG. 9 is a graphical representation of the melting heat flow from DSCas a function of temperature for various plasticized propylene impactcopolymer samples illustrative of the invention;

FIG. 10 is a graphical representation of the crystallization heat flowfrom DSC as a function of temperature for various plasticized propyleneimpact copolymer samples illustrative of the invention;

FIG. 11 is a graphical representation of the shear viscosity as afunction of shear rate for various plasticized propylene homopolymersamples illustrative of the invention;

FIG. 12 is a graphical representation of the shear viscosity as afunction of shear rate for various plasticized propylene copolymersamples illustrative of the invention;

FIG. 13 is a graphical representation of the shear viscosity as afunction of shear rate for various plasticized propylene impactcopolymer samples illustrative of the invention; and

FIG. 14 is a graphical representation of the molecular weightdistribution for various plasticized propylene homopolymer samplesillustrative of the invention.

DEFINITIONS

For purposes of this invention and the claims thereto when a polymer oroligomer is referred to as comprising an olefin, the olefin present inthe polymer or oligomer is the polymerized or oligomerized form of theolefin, respectively. Likewise the use of the term polymer is meant toencompass homopolymers and copolymers. In addition the term copolymerincludes any polymer having 2 or more monomers. Thus, as used herein,the term “polypropylene” means a polymer made of at least 50% propyleneunits, preferably at least 70% propylene units, more preferably at least80% propylene units, even more preferably at least 90% propylene units,even more preferably at least 95% propylene units or 100% propyleneunits. Furthermore, the term “polypropylene” is intended to encompassimpact copolymers

For purposes of this invention an oligomer is defined to have anumber-average molecular weight (M_(n)) of less than 21,000 g/mol,preferably less than 20,000 g/mol, preferably less than 19,000 g/mol,preferably less than 18,000 g/mol, preferably less than 16,000 g/mol,preferably less than 15,000 g/mol, preferably less than 13,000 g/mol,preferably less than 10,000 g/mol, preferably less than 5000 g/mol,preferably less than 3000 g/mol.

For purposes of this invention and the claims thereto Group I, II, andIII basestocks are defined to be mineral oils having the followingproperties:

Saturates (wt %) Sulfur (wt %) Viscosity Index Group I <90 &/or >0.03% &≧80 & <120 Group II ≧90 & ≦0.03% & ≧80 & <120 Group III ≧90 & ≦0.03% &≧120

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to articles formed from plasticized polyolefincompositions comprising one or more polyolefins and one or morenon-functionalized plasticizers (“NFP”).

Typically, the polyolefin(s) are present in the compositions of thepresent invention at from 40 wt % to 99.9 wt % (based upon the weight ofthe polyolefin and the NFP) in one embodiment, and from 50 wt % to 99 wt% in another embodiment, and from 60 wt % to 98 wt % in yet anotherembodiment, and from 70 wt % to 97 wt % in yet another embodiment, andfrom 80 wt % to 97 wt % in yet another embodiment, and from 90 wt % to98 wt % in yet another embodiment, wherein a desirable range may be anycombination of any upper wt % limit with any lower wt % limit describedherein.

In another embodiment the plasticized polyolefin comprises polypropylenepresent at 40 to 99.99 weight %, alternately 50 to 99 weight %,alternately 60 to 99 weight %, alternately 70 to 98 weight %,alternately 80 to 97 weight %, alternately 90 to 96 weight %, and theNFP is present at 60 to 0.01 weight %, alternately 50 to 1 weight %,alternately 40 to 1 weight %, alternately 30 to 2 weight %, alternately20 to 3 weight %, alternately 10 to 4 weight %, based upon the weight ofthe polypropylene and the NFP.

In another embodiment the plasticized polyolefin comprises polybutenepresent at 50 to 99.99 weight %, alternately 60 to 99 weight %,alternately 70 to 98 weight %, alternately 80 to 97 weight %,alternately 90 to 96 weight %, and the NFP is present at 50 to 0.01weight %, alternately 40 to 1 weight %, alternately 30 to 2 weight %,alternately 20 to 3 weight %, alternately 10 to 4 weight %, based uponthe weight of the polybutene and the NFP.

In another embodiment the polyolefin comprises polypropylene and orpolybutene and NFP is present at 0.01 to 50 weight %, more preferably0.05 to 45 weight %, more preferably 0.5 to 40 weight %, more preferably1 to 35 weight %, more preferably 2 to 30 weight %, more preferably 3 to25 weight %, more preferably 4 to 20 weight %, more preferably 5 to 15weight %, based upon the weight of the polypropylene and the NFP. Inanother embodiment, the NFP is present at 1 to 15 weight %, preferably 1to 10 weight %, based upon the weight of the polypropylene and orpolybutene and the NFP.

In another embodiment the NFP is present at more than 3 weight %, basedupon the weight of the polyolefin and the NFP.

For purposes of this invention and the claims thereto the amount of NFPin a given composition is determined by the Extraction method describedbelow. The CRYSTAF method also described is for comparison purposes.

For purposes of this invention and the claims thereto when melting pointis referred to and there is a range of melting temperatures, the meltingpoint is defined to be the peak melting temperature from a differentialscanning calorimetry (DSC) trace as described below.

Non-Functionalized Plasticizer

The polyolefin compositions of the present invention include anon-functionalized plasticizer (“NFP”). The NFP of the present inventionis a compound comprising carbon and hydrogen, and does not include to anappreciable extent functional groups selected from hydroxide, aryls andsubstituted aryls, halogens, alkoxys, carboxylates, esters, carbonunsaturation, acrylates, oxygen, nitrogen, and carboxyl. By “appreciableextent”, it is meant that these groups and compounds comprising thesegroups are not deliberately added to the NFP, and if present at all, arepresent at less than 5 wt % by weight of the NFP in one embodiment, morepreferably less than 4 weight %, more preferably less than 3 weight %,more preferably less than 2 weight %, more preferably less than 1 weight%, more preferably less than 0.7 weight %, more preferably less than 0.5weight %, more preferably less than 0.3 weight %, more preferably lessthan 0.1 weight %, more preferably less than 0.05 weight %, morepreferably less than 0.01 weight %, more preferably less than 0.001weight %, based upon the weight of the NFP.

In one embodiment, the NFP comprises C₆ to C₂₀₀ paraffins, and C₈ toC₁₀₀ paraffins in another embodiment. In another embodiment, the NFPconsists essentially of C₆ to C₂₀₀ paraffins, and consists essentiallyof C₈ to C₁₀₀ paraffins in another embodiment. For purposes of thepresent invention and description herein, the term “paraffin” includesall isomers such as n-paraffins, branched paraffins, isoparaffins, andmay include cyclic aliphatic species, and blends thereof, and may bederived synthetically by means known in the art, or from refined crudeoil in such a way as to meet the requirements described for desirableNFPs described herein. It will be realized that the classes of materialsdescribed herein that are useful as NFPs can be utilized alone oradmixed with other NFPs described herein in order to obtain desiredproperties.

This invention further relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers (“NFP's”) where the non-functionalized plasticizer has akinematic viscosity (“KV”) of 2 cSt or less at 100° C., preferably 1.5cSt or less, preferably 1.0 cSt or less, preferably 0.5 cSt or less (asmeasured by ASTM D 445). In another embodiment the NFP having a KV of 2cSt or less at 100° C. also has a glass transition temperature (Tg) thatcannot be determined by ASTM E 1356 or if it can be determined then theTg according to ASTM E 1356 is less than 30° C. preferably less than 20°C., more preferably less than 10° C., more preferably less than 0° C.,more preferably less than −5° C., more preferably less than −10° C.,more preferably less than −15° C.

In another embodiment the NFP having a KV of 2 cSt or less at 100° C.,optionally having a glass transition temperature (Tg) that cannot bedetermined by ASTM ASTM E 1356 or if it can be determined then the Tgaccording to ASTM E 1356 is less than 30° C. preferably less than 20°C., more preferably less than 10° C., more preferably less than 0° C.,more preferably less than −5° C., has one or more of the followingproperties:

-   1. a distillation range as determined by ASTM D 86 having a    difference between the upper temperature and the lower temperature    of 40° C. or less, preferably 35° C. or less, preferably 30° C. or    less, preferably 25° C. or less, preferably 20° C. or less,    preferably 15° C. or less, preferably 10° C. or less, preferably    between 6 and 40° C., preferably between 6 and 30° C.; and or-   2. an initial boiling point as determined by ASTM D 86 greater than    100° C., preferably greater than 110° C., preferably greater than    120° C., preferably greater than 130° C., preferably greater than    140° C., preferably greater than 150° C., preferably greater than    160° C., preferably greater than 170° C., preferably greater than    180° C., preferably greater than 190° C., preferably greater than    200° C., preferably greater than 210° C., preferably greater than    220° C., preferably greater than 230° C., preferably greater than    240° C.; and or-   3. a pour point of 10° C. or less (as determined by ASTM D 97),    preferably 0° C. or less, preferably −5° C. or less, preferably    −15° C. or less, preferably −40° C. or less, preferably −50° C. or    less, preferably −60° C. or less; and or-   4. a specific gravity (ASTM D 4052, 15.6/15.6° C.) of less than    0.88, preferably less than 0.85, preferably less than 0.80,    preferably less than 0.75, preferably less than 0.70, preferably    from 0.65 to 0.88, preferably from 0.70 to 0.86, preferably from    0.75 to 0.85, preferably from 0.79 to 0.85, preferably from 0.800 to    0.840; and or-   5. a final boiling point as determined by ASTM D 86 of from 115° C.    to 500° C., preferably from 200° C. to 450° C., preferably from    250° C. to 400° C.; and or-   6. a weight average molecular weight (Mw) between 2,000 and 100    g/mol, preferably between 1500 and 150, more preferably between 1000    and 200; and or-   7. a number average molecular weight (Mn) between 2,000 and 100    g/mol, preferably between 1500 and 150, more preferably between 1000    and 200; and or-   8. a flash point as measured by ASTM D 56 of −30 to 150° C., and or-   9. a dielectric constant at 20° C. of less than 3.0, preferably less    than 2.8, preferably less than 2.5, preferably less than 2.3,    preferably less than 2.1; and or-   10. a density (ASTM 4052, 15.6/15.6° C.) of from 0.70 to 0.83 g/cm³;    and or-   11. a kinematic viscosity (ASTM 445, 25° C.) of from 0.5 to 20 cSt    at 25° C.; and or-   12. a carbon number of from 6 to 150, preferably from 7 to 100,    preferably 10 to 30, preferably 12 to 25.

In certain embodiments of the invention the NFP having a KV of 2 cSt orless at 100° C. preferably comprises at least 50 weight %, preferably atleast 60 wt %, preferably at least 70 wt %, preferably at least 80 wt %,preferably at least 90 wt %, preferably at least 95 wt % preferably 100wt % of C₆ to C₁₅₀ isoparaffins, preferably C₆ to C₁₀₀ isoparaffins,preferably C₆ to C₂₅ isoparaffins, more preferably C₈ to C₂₀isoparaffins. By isoparaffin is meant that the paraffin chains possessC₁ to C₁₀ alkyl branching along at least a portion of each paraffinchain. More particularly, the isoparaffins are saturated aliphatichydrocarbons whose molecules have at least one carbon atom bonded to atleast three other carbon atoms or at least one side chain (i.e., amolecule having one or more tertiary or quaternary carbon atoms), andpreferably wherein the total number of carbon atoms per molecule is inthe range between 6 to 50, and between 10 and 24 in another embodiment,and from 10 to 15 in yet another embodiment. Various isomers of eachcarbon number will typically be present. The isoparaffins may alsoinclude cycloparaffins with branched side chains, generally as a minorcomponent of the isoparaffin. Preferably the density (ASTM 4052,15.6/15.6° C.) of these isoparaffins ranges from 0.70 to 0.83 g/cm³; thepour point is −40° C. or less, preferably −50° C. or less, the kinematicviscosity is from 0.5 to 20 cSt at 25° C.; and the average molecularweights in the range of 100 to 300 g/mol. Suitable isoparaffins arecommercially available under the tradename ISOPAR (ExxonMobil ChemicalCompany, Houston Tex.), and are described in, for example, U.S. Pat.Nos. 6,197,285, 3,818,105 and 3,439,088, and sold commercially as ISOPARseries of isoparaffins, some of which are summarized in Table 1.

TABLE 1 ISOPAR Series Isoparaffins kinematic saturates pour Avg.viscosity @ and distillation point Specific 25° C. aromatics Name range(° C.) (° C.) Gravity (cSt) (wt %) ISOPAR E 117-136 −63 0.72 0.85 <0.01ISOPAR G 161-176 −57 0.75 1.46 <0.01 ISOPAR H 178-188 −63 0.76 1.8 <0.01ISOPAR K 179-196 −60 0.76 1.85 <0.01 ISOPAR L 188-207 −57 0.77 1.99<0.01 ISOPAR M 223-254 −57 0.79 3.8 <0.01 ISOPAR V 272-311 −63 0.82 14.8<0.01

In another embodiment, the isoparaffins are a mixture of branched andnormal paraffins having from 6 to 50 carbon atoms, and from 10 to 24carbon atoms in another embodiment, in the molecule. The isoparaffincomposition has a ratio of branch paraffin to n-paraffin ratio (branchparaffin:n-paraffin) ranging from 0.5:1 to 9:1 in one embodiment, andfrom 1:1 to 4:1 in another embodiment. The isoparaffins of the mixturein this embodiment contain greater than 50 wt % (by total weight of theisoparaffin composition) mono-methyl species, for example, 2-methyl,3-methyl, 4-methyl, 5-methyl or the like, with minimum formation ofbranches with substituent groups of carbon number greater than 1, suchas, for example, ethyl, propyl, butyl or the like, based on the totalweight of isoparaffins in the mixture. In one embodiment, theisoparaffins of the mixture contain greater than 70 wt % of themono-methyl species, based on the total weight of the isoparaffins inthe mixture. The isoparaffinic mixture boils within a range of from 100°C. to 350° C. in one embodiment, and within a range of from 110° C. to320° C. in another embodiment. In preparing the different grades, theparaffinic mixture is generally fractionated into cuts having narrowboiling ranges, for example, 35° C. boiling ranges. These branchparaffin/n-paraffin blends are described in, for example, U.S. Pat. No.5,906,727.

Other suitable isoparaffins are also commercial available under thetrade names SHELLSOL (by Shell), SOLTROL (by Chevron Phillips) and SASOL(by Sasol Limited). SHELLSOL is a product of the Royal Dutch/Shell Groupof Companies, for example Shellsol™ (boiling point=215-260° C.). SOLTROLis a product of Chevron Phillips Chemical Co. LP, for example SOLTROL220 (boiling point=233-280° C.). SASOL is a product of Sasol Limited(Johannesburg, South Africa), for example SASOL LPA-210, SASOL-47(boiling point=238-274° C.).

In certain embodiments of the invention the NFP having a KV of 2 cSt orless at 100° C. preferably comprises at least 50 weight %, preferably atleast 60 wt %, preferably at least 70 wt %, preferably at least 80 wt %,preferably at least 90 wt %, preferably at least 95 wt % preferably 100wt % of C₅ to C₂₅ n-paraffins, preferably C₅ to C₂₀ n-paraffins,preferably C₅ to C₁₅ n-paraffins having less than 0.1%, preferably lessthan 0.01% aromatics. In preferred embodiments the n-paraffins have adistillation range of 30° C. or less, preferably 20° C. or less, and oran initial boiling point greater than 150° C., preferably greater than200° C., and or a specific gravity of from 0.65 to 0.85, preferably from0.70 to 0.80, preferably from 0.75 to 0.80, and or a flash point greaterthan 60° C., preferably greater than 90° C., preferably greater than100° C., preferably greater than 120° C.

Suitable n-paraffins are commercially available under the tradenameNORPAR (ExxonMobil Chemical Company, Houston Tex.), and are soldcommercially as NORPAR series of n-paraffins, some of which aresummarized in Table 1a.

TABLE 1a NORPAR Series n-paraffins kinematic saturates pour Avg.viscosity @ and distillation point Specific 25° C. aromatics Name range(° C.) (° C.) Gravity) (cSt) (wt %) NORPAR 12 189-218 0.75 1.6 <0.01NORPAR 13 222-242 0.76 2.4 <0.01 NORPAR 14 241-251 0.77 2.8 <0.01 NORPAR15 249-274 7 0.77 3.3 <0.01

In certain embodiments of the invention the NFP having a KV of 2 cSt orless at 100° C. preferably comprises at least 50 weight %, preferably atleast 60 wt %, preferably at least 70 wt %, preferably at least 80 wt %,preferably at least 90 wt %, preferably at least 95 wt % preferably 100wt % of a dearomaticized aliphatic hydrocarbon comprising a mixture ofnormal paraffins, isoparaffins and cycloparaffins. Typically they are amixture of C₄ to C₂₅ normal paraffins, isoparaffins and cycloparaffins,preferably C₅ to C₁₈, preferably C₅ to C₁₂. They contain very low levelsof aromatic hydrocarbons, preferably less than 0.1, preferably less than0.01 aromatics. In preferred embodiments the dearomatized aliphatichydrocarbons have a distillation range of 30° C. or less, preferably 20°C. or less, and or an initial boiling point greater than 110° C.,preferably greater than 200° C., and or a specific gravity (15.6/15.6°C.) of from 0.65 to 0.85, preferably from 0.70 to 0.85, preferably from0.75 to 0.85, preferably from 0.80 to 0.85 and or a flash point greaterthan 60° C., preferably greater than 90° C., preferably greater than100° C., preferably greater than 110° C.

Suitable dearomatized aliphatic hydrocarbons are commercially availableunder the tradename EXXSOL (ExxonMobil Chemical Company, Houston Tex.),and are sold commercially as EXXSOL series of dearomaticized aliphatichydrocarbons, some of which are summarized in Table 1b.

TABLE 1b EXXSOL Series kinematic saturates pour viscosity @ anddistillation point Avg. Specific 25° C. aromatics Name range (° C.) (°C.) Gravity (cSt) (wt %) EXXSOL isopentane 0.63 0.3 — EXXSOLmethylpentane 59-62 0.66 0.5 — naphtha EXXSOL hexane fluid 66-69 0.670.5 — EXXSOL DSP 75/100 78-99 0.72 0.6 — EXXSOL heptane fluid 94-99 0.700.6 — EXXSOL DSP 90/120  98-115 0.74 Naphtha EXXSOL DSP 115/145 116-1450.75 0.8 — Naphtha EXXSOL D Naphtha 158-178 0.77 1.2 — EXXSOL D 40161-202 0.79 1.4 0.3 EXXSOL D 60 188-210 0.80 0.4 EXXSOL D 80 208-2340.80 2.2 0.4 EXXSOL D 95 224-238 0.80 2.1 0.7 EXXSOL D 110 249-268 0.813.5 0.8 EXXSOL D 130 282-311 −45 0.83 6.9 1.5

This invention also relates to plasticized polyolefin compositionscomprising one or more polyolefins, preferably polypropylene orpolybutene, more preferably polypropylene and one or morenon-functionalized plasticizers where the non-functionalized plasticizercomprises a polyalphaolefin comprising oligomers of C₅ to C₁₄ olefins(preferably C₆ to C₁₄, more preferably C₈ to C₁₂, more preferably C₁₀)having a kinematic viscosity of 5 cSt or more at 100° C., preferably 10cSt or more at 100° C. and a viscosity index of 120 or more, preferably130 or more.

This invention also relates to plasticized polypropylene compositionscomprising polypropylene and one or more non-functionalized plasticizerswhere the non-functionalized plasticizer comprises oligomers of C₆ toC₁₄ olefins having viscosity index of 120 or more, provided that whenthe plasticized composition comprises between 4 and 10 weight % ofpolyalphaolefin that is a hydrogenated, highly branched dimer of analpha olefin having 8-12 carbon atoms, the composition does notcomprises between 18 and 25 weight percent of a linear low densitypolyethylene having a density of 0.912 to 0.935 g/cc.

This invention also relates to plasticized polypropylene compositionscomprising polypropylene and one or more non-functionalized plasticizerswhere the non-functionalized plasticizer comprises oligomers of C₆ toC₁₄ olefins having viscosity index of 120 or more, provided that thepolyolefin does not comprises an impact copolymer of polypropylene and40-50 weight % of an ethylene propylene rubber or provided that thecomposition does not comprise a random copolymer of propylene andethylene.

In another embodiment the NFP comprises polyalphaolefins comprisingoligomers of linear olefins having 5 to 14 carbon atoms, preferably 6 to14 carbon atoms, more preferably 8 to 12 carbon atoms, more preferably10 carbon atoms having a kinematic viscosity of 5 cSt or more at 100°C., preferably 10 cSt or more at 100° C.; and preferably having aviscosity index (“VI”) of 100 or more, preferably 110 or more, morepreferably 120 or more, more preferably 130 or more, more preferably 140or more; and/or having a pour point of −5° C. or less, more preferably−10° C. or less, more preferably −20° C. or less.

In another embodiment polyalphaolefin (PAO) oligomers useful in thepresent invention comprise C₂₀ to C₁₅₀₀ paraffins, preferably C₄₀ toC₁₀₀₀ paraffins, preferably C₅₀ to C₇₅₀ paraffins, preferably C₅₀ toC₅₀₀ paraffins. The PAO oligomers are dimers, trimers, tetramers,pentamers, etc. of C₅ to C₁₄ α-olefins in one embodiment, and C₆ to C₁₂α-olefins in another embodiment, and C₈ to C₁₂ α-olefins in anotherembodiment. Suitable olefins include 1-pentene, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. In oneembodiment, the olefin is 1-decene, and the NFP is a mixture of dimers,trimers, tetramers and pentamers (and higher) of 1-decene. PreferredPAO's are described more particularly in, for example, U.S. Pat. No.5,171,908, and U.S. Pat. No. 5,783,531 and in SYNTHETIC LUBRICANTS ANDHIGH-PERFORMANCE FUNCTIONAL FLUIDS 1-52 (Leslie R. Rudnick & Ronald L.Shubkin, ed. Marcel Dekker, Inc. 1999).

PAO's useful in the present invention typically possess a number averagemolecular weight of from 100 to 21,000 in one embodiment, and from 200to 10,000 in another embodiment, and from 200 to 7,000 in yet anotherembodiment, and from 200 to 2,000 in yet another embodiment, and from200 to 500 in yet another embodiment. Preferred PAO's have kinematicviscosities in the range of 0.1 to 150 cSt at 100° C., and from 0.1 to3000 cSt at 100° C. in another embodiment (ASTM 445). PAO's useful inthe present invention typically have pour points of less than 0° C. inone embodiment, less than −10° C. in another embodiment, and less than−20° C. in yet another embodiment, and less than −40° C. in yet anotherembodiment. Desirable PAO's are commercially available as SpectraSyn(previously SHF and SuperSyn) PAO's (ExxonMobil Chemical Company,Houston Tex.), some of which are summarized in the Table 2 below.

TABLE 2 SHF and SuperSyn Series Polyalphaolefins Kinematic specificgravity viscosity @ Pour Point, PAO (15.6/15.6° C.) 100° C., cSt VI ° C.SHF-20 0.798 1.68 — −63 SHF-21 0.800 1.70 — −57 SHF-23 0.802 1.80 — −54SHF-41 0.818 4.00 123 −57 SHF-61/63 0.826 5.80 133 −57 SHF-82/83 0.8337.90 135 −54 SHF-101 0.835 10.0 136 −54 SHF-403 0.850 40.0 152 −39SHF-1003 0.855 107 179 −33 SuperSyn 2150 0.850 150 214 −42 SuperSyn 23000.852 300 235 −30 SuperSyn 21000 0.856 1,000 305 −18 SuperSyn 230000.857 3,000 388 −9

Other useful PAO's include those sold under the tradenames Synfluid™available from ChevronPhillips Chemical Co. in Pasedena Tex., Durasyn™available from BP Amoco Chemicals in London England, Nexbase™ availablefrom Fortum Oil and Gas in Finland, Synton™ available from CromptonCorporation in Middlebury Conn., USA, EMERY™ available from CognisCorporation in Ohio, USA.

In other embodiments the PAO's have a kinematic viscosity of 10 cSt ormore at 100° C., preferably 30 cSt or more, preferably 50 cSt or more,preferably 80 cSt or more, preferably 110 or more, preferably 150 cSt ormore, preferably 200 cSt or more, preferably 500 cSt or more, preferably750 or more, preferably 1000 cSt or more, preferably 1500 cSt or more,preferably 2000 cSt or more, preferably 2500 or more. In anotherembodiment the PAO's have a kinematic viscosity at 100° C. of between 10cSt and 3000 cSt, preferably between 10 cSt and 1000 cSt, preferablybetween 10 cSt and 40 cSt.

In other embodiments the PAO's have a viscosity index of 120 or more,preferably 130 or more, preferably 140 or more, preferably 150 or more,preferably 170 or more, preferably 190 or more, preferably 200 or more,preferably 250 or more, preferably 300 or more.

In a particularly preferred embodiment the PAO has a kinematic viscosityof 10 cSt or more at 100° C. when the polypropylene is RB 501 F, HifaxCA12A, or ADFLEX Q 100F, as these polymers are described in WO 98/44041.

This invention also relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers where the non-functionalized plasticizer comprises a highpurity hydrocarbon fluid composition comprising a mixture of paraffinshaving 6 to 1500 carbon atoms, preferably 8 to 1000 carbon atoms,preferably 10 to 500 carbon atoms, preferably 12 to about 200 carbonatoms, preferably 14 to 150 carbon atoms, preferably 16 to 100 carbonatoms in the molecule. The hydrocarbon fluid composition has anisoparaffin:n-paraffin ratio ranging from about 0.5:1 to about 9:1,preferably from about 1:1 to about 4:1. The isoparaffins of the mixturecontain greater than fifty percent, 50%, mono-methyl species, e.g.,2-methyl, 3-methyl, 4-methyl, ≧5-methyl or the like, with minimumformation of branches with substituent groups of carbon number greaterthan 1, i.e., ethyl, propyl, butyl or the like, based on the totalweight of isoparaffins in the mixture. Preferably, the isoparaffins ofthe mixture contain greater than 70 percent of the mono-methyl species,based on the total weight of the isoparaffins in the mixture. Thesehydrocarbon fluids preferably have kinematic viscosities KV at 25° C.ranging from 1 to 100,000 cSt, preferably 10 cSt to 2000 cSt and,optionally low pour points typically below −20° C., more preferablybelow −30° C., more preferably ranging from about −20° C. to about −70°C. These hydrocarbon fluids preferably have kinematic viscosities KV at40° C. ranging from 1 to 30,000 cSt, preferably 10 cSt to 2000 cSt and,optionally low pour points typically below −20° C., more preferablybelow −30° C., more preferably ranging from about −20° C. to about −70°C.

This invention also relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers where the non-functionalized plasticizer comprises a linearor branched paraffinic hydrocarbon composition having:

-   1. a number average molecular weight of 500 to 21,000 g/mol;-   2. less than 10% sidechains having 4 or more carbons, preferably    less than 8 weight %, preferably less than 5 weight %, preferably    less than 3 weight %, preferably less than 2 weight %, preferably    less than 1 weight %, preferably less than 0.5 weight %, preferably    less than 0.1 weight %, preferably at less than 0.1 weight %,    preferably at 0.001 weight %;-   3. at least 1 or 2 carbon branches present at 15 weight % or more,    preferably 20 weight % or more, preferably 25 weight % or more,    preferably 30 weight % or more, preferably 35 weight % or more,    preferably 40 weight % or more, preferably 45 weight % or more,    preferably 50 weight % or more,-   4. less than 2.5 weight % cyclic paraffins, preferably less than 2    weight %, preferably less than 1 weight %, preferably less than 0.5    weight %, preferably less than 0.1 weight %, preferably at less than    0.1 weight %, preferably at 0.001 weight %. In additional    embodiments these NFP's have a kinematic viscosity 2 cSt or more at    100° C. and or a VI of 120 or more, preferably 130 or more,    preferably 140 or more, preferably 150 or more, preferably 170 or    more, preferably 190 or more, preferably 200 or more, preferably 250    or more, preferably 300 or more.

In another embodiment the NFP comprises a high purity hydrocarbon fluidcomposition which comprises a mixture of paraffins of carbon numberranging from about C₈ to C₂₀, has a molar ratio ofisoparaffins:n-paraffins ranging from about 0.5:1 to about 9:1, theisoparaffins of the mixture contain greater than 50 percent of themono-methyl species, based on the total weight of the isoparaffins ofthe mixture and wherein the composition has pour points ranging fromabout −20° F. to about −70° F., and kinematic viscosities at 25° C.ranging from about 1 cSt to about 10 cSt.

In another embodiment, the mixture of paraffins has a carbon numberranging from about C₁₀ to about C₁₆. In another embodiment, the mixturecontains greater than 70 percent of the mono-methyl species. In anotherembodiment, the mixture boils at a temperature ranging from about 320°F. to about 650° F. In another embodiment, the mixture boils within arange of from about 350° F. to about 550° F. In another embodiment, themixture comprises a mixture of paraffins of carbon number ranging fromabout C₁₀ to about C₁₆. In another embodiment, the mixture is of carbonnumbers ranging from about C₁₀-C₁₆, the mixture contains greater than 70percent of the mono-methyl species and boils within a range of fromabout 350° F. to about 550° F. In another embodiment, the mixture has amolar ratio of isoparaffins:n-paraffins ranging from about 1:1 to about4:1. In another embodiment, the mixture is derived from aFischer-Tropsch process. Such NFP's may be produced by the methodsdisclosed in U.S. Pat. No. 5,906,727.

Any of the NFP's may also be described by any number of, or anycombination of, parameters described herein. In one embodiment, any ofthe NFP's of the present invention has a pour point (ASTM D97) of lessthan 0° C. in one embodiment, and less than −5° C. in anotherembodiment, and less than −10° C. in another embodiment, less than −20°C. in yet another embodiment, less than −40° C. in yet anotherembodiment, less than −50° C. in yet another embodiment, and less than−60° C. in yet another embodiment, and greater than −120° C. in yetanother embodiment, and greater than −200° C. in yet another embodiment,wherein a desirable range may include any upper pour point limit withany lower pour point limit described herein. In one embodiment, the NFPis a paraffin or other compound having a pour point of less than −30°C., and between −30° C. and −90° C. in another embodiment, in thekinematic viscosity range of from 0.5 to 200 cSt at 40° C. Most mineraloils, which typically include aromatic moieties and other functionalgroups, have a pour point of from 10° C. to −20° C. at the samekinematic viscosity range.

In another embodiment any NFP described herein may have a ViscosityIndex (VI) of 90 or more, preferably 95 or more, more preferably 100 ormore, more preferably 105 or more, more preferably 110 or more, morepreferably 115 or more, more preferably 120 or more, more preferably 125or more, more preferably 130 or more. In another embodiment the NFP hasa VI between 90 and 400, preferably between 120 and 350.

Any NFP described herein may have a dielectric constant at 20° C. ofless than 3.0 in one embodiment, and less than 2.8 in anotherembodiment, less than 2.5 in another embodiment, and less than 2.3 inyet another embodiment, and less than 2.1 in yet another embodiment.Polyethylene and polypropylene each have a dielectric constant (1 kHz,23° C.) of at least 2.3 (CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R.Lide, ed. 82^(d) ed. CRC Press 2001).

In some embodiments, the NFP may have a kinematic viscosity of from 0.1to 3000 cSt at 100° C., and from 0.5 to 1000 cSt at 100° C. in anotherembodiment, and from 1 to 250 cSt at 100° C. in another embodiment, andfrom 1 to 200 cSt at 100° C. in yet another embodiment, and from 10 to500 cSt at 100° C. in yet another embodiment, wherein a desirable rangemay comprise any upper kinematic viscosity limit with any lowerkinematic viscosity limit described herein. In other embodiments the NFPhas a kinematic viscosity of less than 2 cSt at 100° C.

In some embodiments any NFP described herein may have a specific gravity(ASTM D 4052, 15.6/15.6° C.) of less than 0.920 in one embodiment, andless than 0.910 in another embodiment, and from 0.650 to 0.900 inanother embodiment, and from 0.700 to 0.860, and from 0.750 to 0.855 inanother embodiment, and from 0.790 to 0.850 in another embodiment, andfrom 0.800 to 0.840 in yet another embodiment, wherein a desirable rangemay comprise any upper specific gravity limit with any lower specificgravity limit described herein.

In other embodiments any NFP described herein may have a boiling pointof from 100° C. to 500° C. in one embodiment, and from 200° C. to 450°C. in another embodiment, and from 250° C. to 400° C. in yet anotherembodiment. Further, the NFP preferably has a weight average molecularweight of less than 20,000 g/mol in one embodiment, and less than 10,000g/mol in yet another embodiment, and less than 5,000 g/mol in yetanother embodiment, and less than 4,000 g/mol in yet another embodiment,and less than 2,000 g/mol in yet another embodiment, and less than 500g/mol in yet another embodiment, and greater than 100 g/mol in yetanother embodiment, wherein a desirable molecular weight range can beany combination of any upper molecular weight limit with any lowermolecular weight limit described herein.

In another embodiment the NFP comprises a Group III hydrocarbonbasestock. Preferably the NFP comprises a mineral oil having a saturateslevels of 90% or more, preferably 92% or more, preferably 94% or more,preferably 96% or more, preferably 98% or more, preferably 99% or more,and sulfur contents less than 0.03%, preferably between 0.001 and 0.01%and VI is in excess of 120, preferably 130 or more.

In some embodiments, polybutene oligomer liquids are useful as NFP's ofthe present invention. In one embodiment of the invention, thepolybutene processing oil is a low molecular weight (less than 15,000number average molecular weight; less than 60,000 weight averagemolecular weight) homopolymer or copolymer of olefin derived unitshaving from 3 to 8 carbon atoms in one embodiment, preferably from 4 to6 carbon atoms in another embodiment. In yet another embodiment, thepolybutene is a homopolymer or copolymer of a C₄ raffinate. Anembodiment of such low molecular weight polymers termed “polybutene”polymers is described in, for example, SYNTHETIC LUBRICANTS ANDHIGH-PERFORMANCE FUNCTIONAL FLUIDS 357-392 (Leslie R. Rudnick & RonaldL. Shubkin, ed., Marcel Dekker 1999) (hereinafter “polybutene processingoil” or “polybutene”). Another preferred embodiment includespoly(n-butene) hydrocarbons. Preferred poly(n-butenes) have less than15,000 number average molecular weight and less than 60,000 weightaverage molecular weight.

In another preferred embodiment, the polybutene liquid is a copolymer ofat least isobutylene derived units, 1-butene derived units, and 2-butenederived units. In one embodiment, the polybutene liquid is ahomopolymer, copolymer, or terpolymer of the three units, wherein theisobutylene derived units are from 40 to 100 wt % of the copolymer, the1-butene derived units are from 0 to 40 wt % of the copolymer, and the2-butene derived units are from 0 to 40 wt % of the copolymer. Inanother embodiment, the polybutene liquid is a copolymer or terpolymerof the three units, wherein the isobutylene derived units are from 40 to99 wt % of the copolymer, the 1-butene derived units are from 2 to 40 wt% of the copolymer, and the 2-butene derived units are from 0 to 30 wt %of the copolymer. In yet another embodiment, the polybutene liquid is aterpolymer of the three units, wherein the isobutylene derived units arefrom 40 to 96 wt % of the copolymer, the 1-butene derived units are from2 to 40 wt % of the copolymer, and the 2-butene derived units are from 2to 20 wt % of the copolymer. In yet another embodiment, the polybuteneliquid is a homopolymer or copolymer of isobutylene and 1-butene,wherein the isobutylene derived units are from 65 to 100 wt % of thehomopolymer or copolymer, and the 1-butene derived units are from 0 to35 wt % of the copolymer.

Polybutene processing oils useful in the invention typically have anumber average molecular weight (Mn) of less than 10,000 g/mol in oneembodiment, less than 8000 g/mol in another embodiment, and less than6000 g/mol in yet another embodiment. In one embodiment, the polybuteneoil has a number average molecular weight of greater than 400 g/mol, andgreater than 700 g/mol in another embodiment, and greater than 900 g/molin yet another embodiment. A preferred embodiment can be a combinationof any lower molecular weight limit with any upper molecular weightlimit described herein. For example, in one embodiment of the polybuteneof the invention, the polybutene has a number average molecular weightof from 400 g/mol to 10,000 g/mol, and from 700 g/mol to 8000 g/mol inanother embodiment, and from 900 g/mol to 3000 g/mol in yet anotherembodiment. Useful kinematic viscosities of the polybutene processingoil ranges from 10 to 6000 cSt (centiStokes) at 100° C. in oneembodiment, and from 35 to 5000 cSt at 100° C. in another embodiment,and is greater than 35 cSt at 100° C. in yet another embodiment, andgreater than 100 cSt at 100° C. in yet another embodiment.

Commercial examples of useful polybutene liquids include the PARAPOL™Series of processing oils (Infineum, Linden, N.J.), such as PARAPOL™450, 700, 950, 1300, 2400 and 2500 and the Infineum “C” series ofpolybutenes, including C9945, C9900, C9907, C9913, C9922, C9925 aslisted below. The commercially available PARAPOL™ and Infineum Series ofpolybutene processing oils are synthetic liquid polybutenes, eachindividual formulation having a certain molecular weight, allformulations of which can be used in the composition of the invention.The molecular weights of the PARAPOL™ oils are from 420 Mn (PARAPOL™450) to 2700 Mn (PARAPOL™ 2500) as determined by gel permeationchromatography. The MWD of the PARAPOL™ oils range from 1.8 to 3 in oneembodiment, and from 2 to 2.8 in another embodiment; the pour points ofthese polybutenes are less than 25° C. in one embodiment, less than 0°C. in another embodiment, and less than −10° C. in yet anotherembodiment, and between −80° C. and 25° C. in yet another embodiment;and densities (IP 190/86 at 20° C.) range from 0.79 to 0.92 g/cm³, andfrom 0.81 to 0.90 g/cm³ in another embodiment.

Below, Tables 3a and 3b shows some of the properties of the PARAPOL™oils and Infineum oils useful in embodiments of the present invention,wherein the kinematic viscosity was determined as per ASTM D445-97, andthe number average molecular weight (M_(n)) by gel permeationchromatography.

TABLE 3a PARAPOL ™ Grades of polybutenes Kinematic Viscosity @ GradeM_(n) 100° C., cSt 450 420 10.6 700 700 78 950 950 230 1300 1300 6302400 2350 3200 2500 2700 4400

TABLE 3b Infineum Grades of Polybutenes Kinematic Viscosity @ 100° C.,Grade M_(n) cSt Viscosity Index C9945 420 10.6 ~75 C9900 540 11.7 ~60C9907 700 78 ~95 C9995 950 230 ~130 C9913 1300 630 ~175 C9922 2225 2500~230 C9925 2700 4400 ~265

Desirable NFPs for use in the present invention may thus be described byany embodiment described herein, or any combination of the embodimentsdescribed herein. For example, in one embodiment, the NFP is a C₆ toC₂₀₀ paraffin having a pour point of less than −25° C. Described anotherway, the NFP comprises an aliphatic hydrocarbon having a kinematicviscosity of from 0.1 to 1000 cSt at 100° C. Described yet another way,the NFP is selected from n-paraffins, branched isoparaffins, and blendsthereof having from 8 to 25 carbon atoms.

Preferred NFP's of this invention are characterized in that, whenblended with the polyolefin to form a plasticized composition, the NFPis miscible with the polyolefin as indicated by no change in the numberof peaks in the Dynamic Mechanical Thermal Analysis (DMTA) trace ascompared to the unplasticized polyolefin DMTA trace. Lack of miscibilityis indicated by an increase in the number of peaks in DMTA trace overthose in the unplasticized polyolefin. The trace is the plot oftan-delta versus temperature, as described below.

Preferred compositions of the present invention can be characterized inthat the glass transition temperature (T_(g)) of the compositiondecreases by at least 2° C. for every 4 wt % of NFP present in thecomposition in one embodiment; and decreases by at least 3° C. for every4 wt % of NFP present in the composition in another embodiment; anddecreases from at least 4 to 10° C. for every 4 wt % of NFP present inthe composition in yet another embodiment, while the peak melting andcrystallization temperatures of the polyolefin remain constant (within 1to 2° C.). For purpose of this invention and the claims thereto whenglass transition temperature is referred to it is the peak temperaturein the DMTA trace.

Preferred compositions of the present invention can be characterized inthat the glass transition temperature (T_(g)) of the compositiondecreases by at least 2° C. for every 1 wt % of NFP present in thecomposition in one embodiment; preferably by at least 3° C., preferablyby at least 4° C., preferably by at least 5° C., preferably by at least6° C., preferably by at least 7° C., preferably by at least 8° C.,preferably by at least 9° C., preferably by at least 10° C., preferablyby at least 11° C.; preferably while the peak melting and orcrystallization temperatures of the neat polyolefin remain within 1 to5° C. of the plasticized polyolefin, preferably within 1 to 4° C.,preferably within 1 to 3° C., preferably within 1 to 2° C.

Preferred compositions of the present invention can be characterized inthat the glass transition temperature (T_(g)) of the plasticizedcomposition is at least 2° C. lower than that of the neat polyolefin,preferably at least 4° C. lower, preferably at least 6° C. lower,preferably at least 8° C. lower, preferably at least 10° C. lower,preferably at least 15° C. lower, preferably at least 20° C. lower,preferably at least 25° C. lower, preferably at least 30° C. lower,preferably at least 35° C. lower, preferably at least 40° C. lower,preferably at least 45° C. lower.

Preferred compositions of the present invention can be characterized inthat the plasticized composition decreases less than 3%, preferably lessthan 2%, preferably less than 1% in weight when stored at 70° C. for 311hours in a dry oven as determined by ASTM D1203 using a 0.25 mm thicksheet.

Polyolefin

The NFP's described herein are blended with at least one polyolefin toprepare the plasticized compositions of this invention. Preferredpolyolefins include propylene polymers and butene polymers.

In one aspect of the invention, the polyolefin is selected frompolypropylene homopolymer, polypropylene copolymers, and blends thereof.The homopolymer may be atactic polypropylene, isotactic polypropylene,syndiotactic polypropylene and blends thereof. The copolymer can be arandom copolymer, a statistical copolymer, a block copolymer, and blendsthereof. In particular, the inventive polymer blends described hereininclude impact copolymers, elastomers and plastomers, any of which maybe physical blends or in situ blends with the polypropylene and orpolybutene. The method of making the polypropylene or polybutene is notcritical, as it can be made by slurry, solution, gas phase or othersuitable processes, and by using catalyst systems appropriate for thepolymerization of polyolefins, such as Ziegler-Natta-type catalysts,metallocene-type catalysts, other appropriate catalyst systems orcombinations thereof. In a preferred embodiment the propylene polymersand or the butene polymers are made by the catalysts, activators andprocesses described in U.S. Pat. No. 6,342,566, U.S. Pat. No. 6,384,142,WO 03/040201, WO 97/19991 and U.S. Pat. No. 5,741,563. Likewise theimpact copolymers may be prepared by the process described in U.S. Pat.No. 6,342,566, U.S. Pat. No. 6,384,142. Such catalysts are well known inthe art, and are described in, for example, ZIEGLER CATALYSTS (GerhardFink, Rolf Mülhaupt and Hans H. Brintzinger, eds., Springer-Verlag1995); Resconi et al., Selectivity in Propene Polymerization withMetallocene Catalysts, 100 CHEM. REV. 1253-1345 (2000); and I, IIMETALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).

Preferred propylene homopolymers and copolymers useful in this inventiontypically have:

-   1. an Mw of 30,000 to 2,000,000 g/mol preferably 50,000 to    1,000,000, more preferably 90,000 to 500,000, as measured by GPC as    described below in the test methods; and/or-   2. an Mw/Mn of 1 to 40, preferably 1.6 to 20, more preferably 1.8 to    10, more preferably 1.8 to 3 as measured by GPC as described below    in the test methods; and/or-   3. a Tm (second melt) of 30 to 200° C., preferably 30 to 185° C.,    preferably 50 to 175, more preferably 60 to 170 as measured by the    DSC method described below in the test methods; and/or-   4. a crystallinity of 5 to 80%, preferably 10 to 70, more preferably    20 to 60% as measured by the DSC method described below in the test    methods; and/or-   5. a glass transition temperature (Tg) of −40° C. to 20° C.,    preferably −20° C. to 10° C., more preferably −10° C. to 5° C. as    measured by the DMTA method described below in the test methods; and    or-   6. a heat of fusion (Hf) of 180 J/g or less, preferably 20 to 150    J/g, more preferably 40 to 120 J/g as measured by the DSC method    described below in the test methods; and or-   7. a crystallization temperature (Tc) of 15 to 120° C., preferably    20 to 115° C., more preferably 25 to 110° C., preferably 60 to 145°    C., as measured by the method described below in the test methods;    and or-   8. a heat deflection temperature of 45 to 140° C., preferably 60 to    135° C., more preferably 75 to 125° C. as measured by the method    described below in the test methods; and or-   9. a Rockwell hardness (R scale) of 25 or more, preferably 40 or    more, preferably 60 or more, preferably 80 or more, preferably 100    or more, preferably from 25 to 125; and or-   10. a percent crystallinity of at least 30%, preferably at least    40%, alternatively at least 50%, as measured by the DSC method    described below in the test methods; and or-   11. a percent amorphous content of at least 50%, alternatively at    least 60%, alternatively at least 70%, even alternatively between 50    and 95%, or 70% or less, preferably 60% or less, preferably 50% or    less as determined by subtracting the percent crystallinity from    100, and or-   12. a branching index (g′) of 0.2 to 2.0, preferably 0.5 to 1.5,    preferably 0.7 to 1.1, as measured by the GPC method described    below.

The polyolefin may be a propylene homopolymer. In one embodiment thepropylene homopolymer has a molecular weight distribution (Mw/Mn) of upto 40, preferably ranging from 1.5 to 10, and from 1.8 to 7 in anotherembodiment, and from 1.9 to 5 in yet another embodiment, and from 2.0 to4 in yet another embodiment. In another embodiment the propylenehomopolymer has a Gardner impact strength, tested on 0.125 inch disk at23° C., that may range from 20 in-lb to 1000 in-lb in one embodiment,and from 30 in-lb to 500 in-lb in another embodiment, and from 40 in-lbto 400 in-lb in yet another embodiment. In yet another embodiment, the1% secant flexural modulus may range from 100 MPa to 2300 MPa, and from200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPain yet another embodiment, wherein a desirable polyolefin may exhibitany combination of any upper flexural modulus limit with any lowerflexural modulus limit. The melt flow rate (MFR) (ASTM D 1238, 230° C.,2.16 kg) of preferred propylene polymers range from 0.1 dg/min to 2500dg/min in one embodiment, and from 0.3 to 500 dg/min in anotherembodiment.

The polypropylene homopolymer or propylene copolymer useful in thepresent invention may have some level of isotacticity. Thus, in oneembodiment, a polyolefin comprising isotactic polypropylene is a usefulpolymer in the invention of this patent, and similarly, highly isotacticpolypropylene is useful in another embodiment. As used herein,“isotactic” is defined as having at least 10% isotactic pentadsaccording to analysis by ¹³C-NMR as described in the test methods below.As used herein, “highly isotactic” is defined as having at least 60%isotactic pentads according to analysis by ¹³C-NMR. In a desirableembodiment, a polypropylene homopolymer having at least 85% isotacticityis the polyolefin, and at least 90% isotacticity in yet anotherembodiment.

In another desirable embodiment, a polypropylene homopolymer having atleast 85% syndiotacticity is the polyolefin, and at least 90%syndiotacticity in yet another embodiment. As used herein,“syndiotactic” is defined as having at least 10% syndiotactic pentadsaccording to analysis by ¹³C-NMR as described in the test methods below.As used herein, “highly syndiotactic” is defined as having at least 60%syndiotactic pentads according to analysis by ¹³C-NMR.

In another embodiment the propylene homoploymer may be isotactic, highlyisotactic, syndiotactic, highly syndiotactic or atactic. Atacticpolypropylene is defined to be less than 10% isotactic or syndiotacticpentads. Preferred atactic polypropylenes typically have an Mw of 20,000up to 1,000,000.

Preferred propylene polymers that are useful in this invention includethose sold under the tradenames ACHIEVE™ and ESCORENE™ by ExxonMobilChemical Company in Houston Tex.

In another embodiment of the invention, the polyolefin is a propylenecopolymer, either random, or block, of propylene derived units and unitsselected from ethylene and C₄ to C₂₀ α-olefin derived units, typicallyfrom ethylene and C₄ to C₁₀ α-olefin derived units in anotherembodiment. The ethylene or C₄ to C₂₀ α-olefin derived units are presentfrom 0.1 wt % to 50 wt % of the copolymer in one embodiment, and from0.5 to 30 wt % in another embodiment, and from 1 to 15 wt % in yetanother embodiment, and from 0.1 to 5 wt % in yet another embodiment,wherein a desirable copolymer comprises ethylene and C₄ to C₂₀ α-olefinderived units in any combination of any upper wt % limit with any lowerwt % limit described herein. The propylene copolymer will have a weightaverage molecular weight of from greater than 8,000 g/mol in oneembodiment, and greater than 10,000 g/mol in another embodiment, andgreater than 12,000 g/mol in yet another embodiment, and greater than20,000 g/mol in yet another embodiment, and less than 1,000,000 g/mol inyet another embodiment, and less than 800,000 in yet another embodiment,wherein a desirable copolymer may comprise any upper molecular weightlimit with any lower molecular weight limit described herein.

Particularly desirable propylene copolymers have a molecular weightdistribution (Mw/Mn) ranging from 1.5 to 10, and from 1.6 to 7 inanother embodiment, and from 1.7 to 5 in yet another embodiment, andfrom 1.8 to 4 in yet another embodiment. The Gardner impact strength,tested on 0.125 inch disk at 23° C., of the propylene copolymer mayrange from 20 in-lb to 1000 in-lb in one embodiment, and from 30 in-lbto 500 in-lb in another embodiment, and from 40 in-lb to 400 in-lb inyet another embodiment. In yet another embodiment, the 1% secantflexural modulus of the propylene copolymer ranges from 100 MPa to 2300MPa, and from 200 MPa to 2100 MPa in another embodiment, and from 300MPa to 2000 MPa in yet another embodiment, wherein a desirablepolyolefin may exhibit any combination of any upper flexural moduluslimit with any lower flexural modulus limit. The melt flow rate (MFR) ofpropylene copolymer ranges from 0.1 dg/min to 2500 dg/min in oneembodiment, and from 0.3 to 500 dg/min in another embodiment.

In another embodiment the polyolefin may be a propylene copolymercomprising propylene and one or more other monomers selected from thegroup consisting of ethylene and C₄ to C₂₀ linear, branched or cyclicmonomers, and in some embodiments is a C₄ to C₁₂ linear or branchedalpha-olefin, preferably butene, pentene, hexene, heptene, octene,nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl-hexene-1, and the like. The monomers may bepresent at up to 50 weight %, preferably from 0 to 40 weight %, morepreferably from 0.5 to 30 weight %, more preferably from 2 to 30 weight%, more preferably from 5 to 20 weight %.

In a preferred embodiment the butene homopolymers and copolymers usefulin this invention typically have:

-   1. an Mw of 30,000 to 2,000,000 g/mol preferably 50,000 to    1,000,000, more preferably 90,000 to 500,000, as measured by GPC as    described below in the test methods; and/or-   2. an Mw/Mn of 1 to 40, preferably 1.6 to 20, more preferably 1.8 to    10, more preferably 1.8 to 3 as measured by GPC as described below    in the test methods; and/or-   3. a Tm (second melt) of 30 to 150° C., preferably 30 to 145° C.,    preferably 50 to 135, as measured by the DSC method described below    in the test methods; and/or-   4. a crystallinity of 5 to 80%, preferably 10 to 70, more preferably    20 to 60% as measured by the DSC method described below in the test    methods; and/or-   5. a glass transition temperature (Tg) of −50° C. to 0° C. as    measured by the DMTA method described below in the test methods; and    or-   6. a heat of fusion (Hf) of 180 J/g or less, preferably 20 to 150    J/g, more preferably 40 to 120 J/g as measured by the DSC method    described below in the test methods; and or-   7. a crystallization temperature (Tc) of 10 to 130° C., preferably    20 to 115° C., more preferably 25 to 110° C., preferably 60 to 145°    C., as measured by the DSC method described below in the test    methods; and or-   8. a percent amorphous content of at least 50%, alternatively at    least 60%, alternatively at least 70%, even alternatively between 50    and 95%, or 70% or less, preferably 60% or less, preferably 50% or    less as determined by subtracting the percent crystallinity from    100, and or-   9. A branching index (g′) of 0.2 to 2.0, preferably 0.5 to 1.5,    preferably 0.7 to 1.1, as measured by the GPC method described    below.

Preferred linear alpha-olefins useful as comonomers for the propylenecopolymers useful in this invention include C₃ to C₈ alpha-olefins, morepreferably 1-butene, 1-hexene, and 1-octene, even more preferably1-butene. Preferred linear alpha-olefins useful as comonomers for thebutene copolymers useful in this invention include C₃ to C₈alpha-olefins, more preferably propylene, 1-hexene, and 1-octene, evenmore preferably propylene. Preferred branched alpha-olefins include4-methyl-1-pentene, 3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene,5-ethyl-1-nonene. Preferred aromatic-group-containing monomers containup to 30 carbon atoms. Suitable aromatic-group-containing monomerscomprise at least one aromatic structure, preferably from one to three,more preferably a phenyl, indenyl, fluorenyl, or naphthyl moiety. Thearomatic-group-containing monomer further comprises at least onepolymerizable double bond such that after polymerization, the aromaticstructure will be pendant from the polymer backbone. The aromatic-groupcontaining monomer may further be substituted with one or morehydrocarbyl groups including but not limited to C₁ to C₁₀ alkyl groups.Additionally two adjacent substitutions may be joined to form a ringstructure. Preferred aromatic-group-containing monomers contain at leastone aromatic structure appended to a polymerizable olefinic moiety.Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,paramethyl styrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclicgroup containing monomers preferably have at least one polymerizableolefinic group that is either pendant on the cyclic structure or is partof the cyclic structure. The cyclic structure may also be furthersubstituted by one or more hydrocarbyl groups such as, but not limitedto, C₁ to C₁₀ alkyl groups. Preferred non-aromatic cyclic groupcontaining monomers include vinylcyclohexane, vinylcyclohexene,vinylnorbornene, ethylidene norbornene, cyclopentadiene, cyclopentene,cyclohexene, cyclobutene, vinyladamantane and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃0, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

In a preferred embodiment one or more dienes are present in the polymerproduced herein at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

In yet another embodiment, the Gardner impact strength, tested on 0.125inch disk at 23° C., of the butene copolymer ranges from 20 in-lb to1000 in-lb, and from 30 in-lb to 500 in-lb in another embodiment, andfrom 40 in-lb to 400 in-lb in yet another embodiment. Further, thebutene copolymer may possess a 1% secant flexural modulus ranging from100 MPa to 2300 MPa, and from 200 MPa to 2100 MPa in another embodiment,and from 300 MPa to 2000 MPa in yet another embodiment, wherein adesirable polyolefin may exhibit any combination of any upper flexuralmodulus limit with any lower flexural modulus limit. The melt flow rate(MFR) of desirable copolymers ranges from 0.1 dg/min to 2500 dg/min inone embodiment, and from 0.1 to 500 dg/min in another embodiment.

In another embodiment the propylene copolymer is a random copolymer,also known as an “RCP,” comprising propylene and up to 20 mole % ofethylene or a C₄ to C₂₀ olefin, preferably up to 20 mole % ethylene.

In another embodiment, the polyolefin may be an impact copolymer (ICP)or block copolymer. Propylene impact copolymers are commonly used in avariety of applications where strength and impact resistance are desiredsuch as molded and extruded automobile parts, household appliances,luggage and furniture. Propylene homopolymers alone are often unsuitablefor such applications because they are too brittle and have low impactresistance particularly at low temperature, whereas propylene impactcopolymers are specifically engineered for applications such as these.

A typical propylene impact copolymer contains at least two phases orcomponents, e.g., a homopolymer component and a copolymer component. Theimpact copolymer may also comprise three phases such as a PP/EP/PEcombination with the PP continuous and a dispersed phase with EP outsideand PE inside the dispersed phase particles. These components areusually produced in a sequential polymerization process wherein thehomopolymer produced in a first reactor is transferred to a secondreactor where copolymer is produced and incorporated within the matrixof the homopolymer component. The copolymer component has rubberycharacteristics and provides the desired impact resistance, whereas thehomopolymer component provides overall stiffness.

Another important feature of ICP's is the amount of amorphouspolypropylene they contain. The ICP's of this invention arecharacterized as having low amorphous polypropylene, preferably lessthan 3% by weight, more preferably less than 2% by weight, even morepreferably less than 1% by weight and most preferably there is nomeasurable amorphous polypropylene. Percent amorphous polypropylene isdetermined by the method described below in the test methods.

Preferred impact copolymers may be a reactor blend (in situ blend) or apost reactor (ex-situ) blend. In one embodiment, a suitable impactcopolymer comprises from 40% to 95% by weight Component A and from 5% to60% by weight Component B based on the total weight of the impactcopolymer; wherein Component A comprises propylene homopolymer orcopolymer, the copolymer comprising 10% or less by weight ethylene,butene, hexene or octene comonomer; and wherein Component B comprisespropylene copolymer, wherein the copolymer comprises from 5% to 70% byweight ethylene, butene, hexene and/or octene comonomer, and from about95% to about 30% by weight propylene. In one embodiment of the impactcopolymer, Component B consists essentially of propylene and from about30% to about 65% by weight ethylene. In another embodiment, Component Bcomprises ethylene-propylene copolymers, ethylene-propylene-dieneterpolymers, ethylene-acrylate copolymers, ethylene-vinyl acetate,styrene-butadiene copolymers, ethylene-acrylic ester copolymers,polybutadiene, polyisoprene, natural rubber, isobutylene, hydrocarbonresin (the hydrocarbon resin being characterized by a molecular weightless than 5000, a T_(g) of about 50 to 100° C. and a softening point,Ring and Ball, as measured by ASTM E-28, of less than about 140° C.),rosin ester, and mixtures thereof. In another embodiment, Component Bhas a molecular weight distribution of less than 3.5. In yet anotherembodiment, Component B has a weight average molecular weight of atleast 20,000. A useful impact copolymer is disclosed in, for example,U.S. Pat. No. 6,342,566 and U.S. Pat. No. 6,384,142.

Component B is most preferably a copolymer consisting essentially ofpropylene and ethylene although other propylene copolymers, ethylenecopolymers or terpolymers may be suitable depending on the particularproduct properties desired. For example, propylene/butene, hexene oroctene copolymers, and ethylene/butene, hexene or octene copolymers maybe used, and propylene/ethylene/hexene-1 terpolymers may be used. In apreferred embodiment though, Component B is a copolymer comprising atleast 40% by weight propylene, more preferably from about 80% by weightto about 30% by weight propylene, even more preferably from about 70% byweight to about 35% by weight propylene. The comonomer content ofComponent B is preferably in the range of from about 20% to about 70% byweight comonomer, more preferably from about 30% to about 65% by weightcomonomer, even more preferably from about 35% to about 60% by weightcomonomer. Most preferably Component B consists essentially of propyleneand from about 20% to about 70% ethylene, more preferably from about 30%to about 65% ethylene, and most preferably from about 35% to about 60%ethylene.

For other Component B copolymers, the comonomer contents will need to beadjusted depending on the specific properties desired. For example, forethylene/hexene copolymers, Component B should contain at least 17% byweight hexene and at least 83% by weight ethylene.

Component B, preferably has a narrow molecular weight distribution Mw/Mn(“MWD”), i.e., lower than 5.0, preferably lower than 4.0, morepreferably lower than 3.5, even more preferably lower than 3.0 and mostpreferably 2.5 or lower. These molecular weight distributions should beobtained in the absence of visbreaking or peroxide or other post reactortreatment molecular weight tailoring. Component B preferably has aweight average molecular weight (Mw as determined by GPC) of at least100,000, preferably at least 150,000, and most preferably at least200,000.

Component B preferably has an intrinsic viscosity greater than 1.00dl/g, more preferably greater than 1.50 dl/g and most preferably greaterthan 2.00 dl/g. The term “intrinsic viscosity” or “IV” is usedconventionally herein to mean the viscosity of a solution of polymersuch as Component B in a given solvent at a given temperature, when thepolymer composition is at infinite dilution. According to the ASTMstandard test method D 1601-78, IV measurement involves a standardcapillary viscosity measuring device, in which the viscosity of a seriesof concentrations of the polymer in the solvent at the given temperatureare determined. For Component B, decalin is a suitable solvent and atypical temperature is 135° C. From the values of the viscosity ofsolutions of varying concentrations, the “value” at infinite dilutioncan be determined by extrapolation.

Component B preferably has a composition distribution breadth index(CDBI) of greater than 60%, more preferably greater than 65%, even morepreferably greater than 70%, even more preferably greater than 75%,still more preferably greater than 80%, and most preferably greater than85%. CDBI characterizes the compositional variation among polymer chainsin terms of ethylene (or other comonomer) content of the copolymer as awhole. The CDBI is defined in U.S. Pat. No. 5,382,630, which is herebyincorporate by reference, as the weight percent of the copolymermolecules having a comonomer content within 50% of the median totalmolar comonomer content. The CDBI of a copolymer is readily determinedutilizing well known techniques for isolating individual fractions of asample of the copolymer. One such technique is Temperature RisingElution Fraction (TREF), as described in Wild, et al., J. Poly. Sci.Poly. Phys. Ed., vol. 20, p. 441 (1982) and U.S. Pat. No. 5,008,204,which are incorporated herein by reference.

Component B of the ICP's preferably has low crystallinity, preferablyless than 10% by weight of a crystalline portion, more preferably lessthan 5% by weight of a crystalline portion. Where there is a crystallineportion of Component B, its composition is preferably the same as or atleast similar to (within 15% by weight) the remainder of Component B interms of overall comonomer weight percent.

The preferred melt flow rate (“MFR”) of these ICP's depends on thedesired end use but is typically in the range of from about 0.2 dg/minto about 200 dg/min, more preferably from about 5 dg/min to about 100dg/min. Significantly, high MFRs, i.e., higher than 50 dg/min areobtainable. The ICP preferably has a peak melting point (Tm) of at least145° C., preferably at least 150° C., more preferably at least 152° C.,and most preferably at least 155° C.

The ICP's comprise from about 40% to about 95% by weight Component A andfrom about 5% to about 60% by weight Component B, preferably from about50% to about 95% by weight Component A and from about 5% to about 50%Component B, even more preferably from about 60% to about 90% by weightComponent A and from about 10% to about 40% by weight Component B. Inthe most preferred embodiment, the ICP consists essentially ofComponents A and B. The overall comonomer (preferably ethylene) contentof the total ICP is preferably in the range of from about 2% to about30% by weight, preferably from about 5% to about 25% by weight, evenmore preferably from about 5% to about 20% by weight, still morepreferably from about 5% to about 15% by weight comonomer.

In another embodiment a preferred impact copolymer composition isprepared by selecting Component A and Component B such that theirrefractive indices (as measured by ASTM D 542-00) are within 20% of eachother, preferably within 15%, preferably 10, even more preferably within5% of each other. This selection produces impact copolymers withoutstanding clarity. In another embodiment a preferred impact copolymercomposition is prepared by selecting a blend of Component A and an NFPand a blend of Component B and an NFP such that refractive indices ofthe blends (as measured by ASTM D 542-00) are within 20% of each other,preferably within 15%, preferably 10, even more preferably within 5% ofeach other.

In yet another embodiment, the Gardner impact strength, tested on 0.125inch disk at −29° C., of the propylene impact copolymer ranges from 20in-lb to 1000 in-lb, and from 30 in-lb to 500 in-lb in anotherembodiment, and from 40 in-lb to 400 in-lb in yet another embodiment.Further, the 1% secant flexural modulus of the propylene impactcopolymer may range from 100 MPa to 2300 MPa in one embodiment, and from200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPain yet another embodiment, wherein a desirable polyolefin may exhibitany combination of any upper flexural modulus limit with any lowerflexural modulus limit. The melt flow rate (MFR) of desirablehomopolymers ranges from 0.1 dg/min to 2500 dg/min in one embodiment,and from 0.3 to 500 dg/min in another embodiment.

Another suitable polyolefin comprises a blend of a polypropylenehomopolymer or propylene copolymer with a plastomer. The plastomers thatare useful in the present invention may be described as polyolefincopolymers having a density of from 0.85 to 0.915 g/cm³ ASTM D 4703Method B and ASTM D 1505—the first of these is compression molding at acooling rate of 15° C./min and the second is the Gradient Density Columnmethod for density determination and a melt index (MI) between 0.10 and30 dg/min (ASTM D 1238; 190° C., 2.1 kg). In one embodiment, the usefulplastomer is a copolymer of ethylene derived units and at least one ofC₃ to C₁₀ α-olefin derived units, the copolymer having a density lessthan 0.915 g/cm³. The amount of comonomer (C₃ to C₁₀ α-olefin derivedunits) present in the plastomer ranges from 2 wt % to 35 wt % in oneembodiment, and from 5 wt % to 30 wt % in another embodiment, and from15 wt % to 25 wt % in yet another embodiment, and from 20 wt % to 30 wt% in yet another embodiment.

The plastomer useful in the invention has a melt index (MI) of between0.10 and 20 dg/min in one embodiment, and from 0.2 to 10 dg/min inanother embodiment, and from 0.3 to 8 dg/min in yet another embodiment.The average molecular weight of useful plastomers ranges from 10,000 to800,000 in one embodiment, and from 20,000 to 700,000 in anotherembodiment. The 1% secant flexural modulus (ASTM D 790) of usefulplastomers ranges from 10 MPa to 150 MPa in one embodiment, and from 20MPa to 100 MPa in another embodiment. Further, the plastomer that isuseful in compositions of the present invention has a meltingtemperature (T_(m)) of from 30 to 80° C. (first melt peak) and from 50to 125° C. (second melt peak) in one embodiment, and from 40 to 70° C.(first melt peak) and from 50 to 100° C. (second melt peak) in anotherembodiment.

Plastomers useful in the present invention are metallocene catalyzedcopolymers of ethylene derived units and higher α-olefin derived unitssuch as propylene, 1-butene, 1-hexene and 1-octene, and which containenough of one or more of these comonomer units to yield a densitybetween 0.860 and 0.900 g/cm³ in one embodiment. The molecular weightdistribution (Mw/Mn) of desirable plastomers ranges from 1.5 to 5 in oneembodiment, and from 2.0 to 4 in another embodiment. Examples of acommercially available plastomers are EXACT 4150, a copolymer ofethylene and 1-hexene, the 1-hexene derived units making up from 18 to22 wt % of the plastomer and having a density of 0.895 g/cm³ and MI of3.5 dg/min (ExxonMobil Chemical Company, Houston, Tex.); and EXACT 8201,a copolymer of ethylene and 1-octene, the 1-octene derived units makingup from 26 to 30 wt % of the plastomer, and having a density of 0.882g/cm³ and MI of 1.0 dg/min (ExxonMobil Chemical Company, Houston, Tex.).

In another embodiment polymers that are useful in this invention includehomopolymers and random copolymers of propylene having a heat of fusionas determined by Differential Scanning Calorimetry (DSC) of less than 50J/g, a melt index (MI) of less than 20 dg/min and or an MFR of 20 dg/minor less, and contains stereoregular propylene crystallinity preferablyisotactic stereoregular propylene crystallinity. In another embodimentthe polymer is a random copolymer of propylene and at least onecomonomer selected from ethylene, C₄-C₁₂ α-olefins, and combinationsthereof. Preferably the random copolymers of propylene comprises from 2wt % to 25 wt % polymerized ethylene units, based on the total weight ofthe polymer; has a narrow composition distribution; has a melting point(Tm) of from 25° C. to 120° C., or from 35° C. to 80° C.; has a heat offusion within the range having an upper limit of 50 J/g or 25 J/g and alower limit of 1 J/g or 3 J/g; has a molecular weight distribution Mw/Mnof from 1.8 to 4.5; and has a melt index (MI) of less than 20 dg/min, orless than 15 dg/min. The intermolecular composition distribution of thecopolymer is determined by thermal fractionation in a solvent. A typicalsolvent is a saturated hydrocarbon such as hexane or heptane. Thethermal fractionation procedure is described below. Typically,approximately 75% by weight, preferably 85% by weight, of the copolymeris isolated as one or two adjacent, soluble fractions with the balanceof the copolymer in immediately preceding or succeeding fractions. Eachof these fractions has a composition (wt % comonomer such as ethylene orother α-olefin) with a difference of no greater than 20% (relative),preferably 10% (relative), of the average weight % comonomer of thecopolymer. The copolymer has a narrow composition distribution if itmeets the fractionation test described above.

A particularly preferred polymer useful in the present invention is anelastic polymer with a moderate level of crystallinity due tostereoregular propylene sequences. The polymer can be: (A) a propylenehomopolymer in which the stereoregularity is disrupted in some mannersuch as by regio-inversions; (B) a random propylene copolymer in whichthe propylene stereoregularity is disrupted at least in part bycomonomers; or (C) a combination of (A) and (B).

In one embodiment, the polymer further includes a non-conjugated dienemonomer to aid in vulcanization and other chemical modification of theblend composition. The amount of diene present in the polymer ispreferably less than 10% by weight, and more preferably less than 5% byweight. The diene may be any non-conjugated diene which is commonly usedfor the vulcanization of ethylene propylene rubbers including, but notlimited to, ethylidene norbornene, vinyl norbornene, anddicyclopentadiene.

In one embodiment, the polymer is a random copolymer of propylene and atleast one comonomer selected from ethylene, C₄-C₁₂ α-olefins, andcombinations thereof. In a particular aspect of this embodiment, thecopolymer includes ethylene-derived units in an amount ranging from alower limit of 2%, 5%, 6%, 8%, or 10% by weight to an upper limit of20%, 25%, or 28% by weight. This embodiment will also includepropylene-derived units present in the copolymer in an amount rangingfrom a lower limit of 72%, 75%, or 80% by weight to an upper limit of98%, 95%, 94%, 92%, or 90% by weight. These percentages by weight arebased on the total weight of the propylene and ethylene-derived units;i.e., based on the sum of weight percent propylene-derived units andweight percent ethylene-derived units being 100%. The ethylenecomposition of a polymer can be measured as follows. A thin homogeneousfilm is pressed at a temperature of about 150° C. or greater, thenmounted on a Perkin Elmer PE 1760 infrared spectrophotometer. A fullspectrum of the sample from 600 cm⁻¹ to 4000 cm⁻¹ is recorded and themonomer weight percent of ethylene can be calculated according to thefollowing equation: Ethylene wt %=82.585−111.987X+30.045 X², wherein Xis the ratio of the peak height at 1155 cm⁻¹ and peak height at either722 cm⁻¹ or 732 cm⁻¹, whichever is higher. The concentrations of othermonomers in the polymer can also be measured using this method.

Comonomer content of discrete molecular weight ranges can be measured byFourier Transform Infrared Spectroscopy (FTIR) in conjunction withsamples collected by GPC. One such method is described in Wheeler andWillis, Applied Spectroscopy, 1993, vol. 47, pp. 1128-1130. Differentbut similar methods are equally functional for this purpose and wellknown to those skilled in the art.

Comonomer content and sequence distribution of the polymers can bemeasured by ¹³C nuclear magnetic resonance (¹³C NMR), and such method iswell known to those skilled in the art.

In one embodiment, the polymer is a random propylene copolymer having anarrow composition distribution. In another embodiment, the polymer is arandom propylene copolymer having a narrow composition distribution anda melting point of from 25° C. to 110° C. The copolymer is described asrandom because for a polymer comprising propylene, comonomer, andoptionally diene, the number and distribution of comonomer residues isconsistent with the random statistical polymerization of the monomers.In stereoblock structures, the number of block monomer residues of anyone kind adjacent to one another is greater than predicted from astatistical distribution in random copolymers with a similarcomposition. Historical ethylene-propylene copolymers with stereoblockstructure have a distribution of ethylene residues consistent with theseblocky structures rather than a random statistical distribution of themonomer residues in the polymer. The intramolecular compositiondistribution (i.e., randomness) of the copolymer may be determined by¹³C NMR, which locates the comonomer residues in relation to theneighbouring propylene residues. The intermolecular compositiondistribution of the copolymer is determined by thermal fractionation ina solvent. A typical solvent is a saturated hydrocarbon such as hexaneor heptane. Typically, approximately 75% by weight, preferably 85% byweight, of the copolymer is isolated as one or two adjacent, solublefractions with the balance of the copolymer in immediately preceding orsucceeding fractions. Each of these fractions has a composition (wt %comonomer such as ethylene or other α-olefin) with a difference of nogreater than 20% (relative), preferably 10% (relative), of the averageweight % comonomer of the copolymer. The copolymer has a narrowcomposition distribution if it meets the fractionation test describedabove. To produce a copolymer having the desired randomness and narrowcomposition, it is beneficial if (1) a single sited metallocene catalystis used which allows only a single statistical mode of addition of thefirst and second monomer sequences and (2) the copolymer is well-mixedin a continuous flow stirred tank polymerization reactor which allowsonly a single polymerization environment for substantially all of thepolymer chains of the copolymer.

The crystallinity of the polymers may be expressed in terms of heat offusion. Embodiments of the present invention include polymers having aheat of fusion, as determined by DSC, ranging from a lower limit of 1.0J/g, or 3.0 J/g, to an upper limit of 50 J/g, or 10 J/g. Without wishingto be bound by theory, it is believed that the polymers of embodimentsof the present invention have generally isotactic crystallizablepropylene sequences, and the above heats of fusion are believed to bedue to the melting of these crystalline segments.

The crystallinity of the polymer may also be expressed in terms ofcrystallinity percent. The thermal energy for the highest order ofpolypropylene is estimated at 207 J/g. That is, 100% crystallinity isequal to 207 J/g. Preferably, the polymer has a polypropylenecrystallinity within the range having an upper limit of 65%, 40%, 30%,25%, or 20%, and a lower limit of 1%, 3%, 5%, 7%, or 8%.

The level of crystallinity is also reflected in the melting point. Theterm “melting point,” as used herein, is the highest peak highestmeaning the largest amount of polymer being reflected as opposed to thepeak occurring at the highest temperature among principal and secondarymelting peaks as determined by DSC, discussed above. In one embodimentof the present invention, the polymer has a single melting point.Typically, a sample of propylene copolymer will show secondary meltingpeaks adjacent to the principal peak, which are considered together as asingle melting point. The highest of these peaks is considered themelting point. The polymer preferably has a melting point by DSC rangingfrom an upper limit of 110° C., 105° C., 90° C., 80° C., or 70° C., to alower limit of 0° C., 20° C., 25° C., 30° C., 35° C., 40° C., or 45° C.

Such polymers used in the invention have a weight average molecularweight (Mw) within the range having an upper limit of 5,000,000 g/mol,1,000,000 g/mol, or 500,000 g/mol, and a lower limit of 10,000 g/mol,20,000 g/mol, or 80,000 g/mol, and a molecular weight distribution Mw/Mn(MWD), sometimes referred to as a “polydispersity index” (PDI), rangingfrom a lower limit of 1.5, 1.8, or 2.0 to an upper limit of 40, 20, 10,5, or 4.5. In one embodiment, the polymer has a Mooney viscosity,ML(1+4) @ 125° C., of 100 or less, 75 or less, 60 or less, or 30 orless. Mooney viscosity, as used herein, can be measured as ML(1+4) @125° C. according to ASTM D1646, unless otherwise specified.

The polymers used in embodiments of the present invention can have atacticity index (m/r) ranging from a lower limit of 4 or 6 to an upperlimit of 8, 10, or 12. The tacticity index, expressed herein as “m/r”,is determined by ¹³C nuclear magnetic resonance (NMR). The tacticityindex m/r is calculated as defined in H. N. Cheng, Macromolecules, 17,1950 (1984). The designation “m” or “r” describes the stereochemistry ofpairs of contiguous propylene groups, “m” referring to meso and “r” toracemic. An m/r ratio of 0 to less than 1.0 generally describes asyndiotactic polymer, and an m/r ratio of 1.0 an atactic material, andan m/r ratio of greater than 1.0 an isotactic material. An isotacticmaterial theoretically may have a ratio approaching infinity, and manyby-product atactic polymers have sufficient isotactic content to resultin ratios of greater than 50.

In one embodiment, the polymer has isotactic stereoregular propylenecrystallinity. The term “stereoregular” as used herein means that thepredominant number, i.e. greater than 80%, of the propylene residues inthe polypropylene or in the polypropylene continuous phase of a blend,such as impact copolymer exclusive of any other monomer such asethylene, has the same 1,2 insertion and the stereochemical orientationof the pendant methyl groups is the same, either meso or racemic.

An ancillary procedure for the description of the tacticity of thepropylene units of embodiments of the current invention is the use oftriad tacticity. The triad tacticity of a polymer is the relativetacticity of a sequence of three adjacent propylene units, a chainconsisting of head to tail bonds, expressed as a binary combination of mand r sequences. It is usually expressed for copolymers of the presentinvention as the ratio of the number of units of the specified tacticityto all of the propylene triads in the copolymer.

The triad tacticity (mm fraction) of a propylene copolymer can bedetermined from a ¹³C NMR spectrum of the propylene copolymer and thefollowing formula:

${{mm}\mspace{14mu} {Fraction}} = \frac{{PPP}({mm})}{{{PPP}({mm})} + {{PPP}({mr})} + {{PPP}({rr})}}$

where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from themethyl groups of the second units in the following three propylene unitchains consisting of head-to-tail bonds:

The ¹³C NMR spectrum of the propylene copolymer is measured as describedin U.S. Pat. No. 5,504,172. The spectrum relating to the methyl carbonregion (19-23 parts per million (ppm)) can be divided into a firstregion (21.2-21.9 ppm), a second region (20.3-21.0 ppm) and a thirdregion (19.5-20.3 ppm). Each peak in the spectrum was assigned withreference to an article in the journal Polymer, Volume 30 (1989), page1350. In the first region, the methyl group of the second unit in thethree propylene unit chain represented by PPP (mm) resonates. In thesecond region, the methyl group of the second unit in the threepropylene unit chain represented by PPP (mr) resonates, and the methylgroup (PPE-methyl group) of a propylene unit whose adjacent units are apropylene unit and an ethylene unit resonates (in the vicinity of 20.7ppm). In the third region, the methyl group of the second unit in thethree propylene unit chain represented by PPP (rr) resonates, and themethyl group (EPE-methyl group) of a propylene unit whose adjacent unitsare ethylene units resonates (in the vicinity of 19.8 ppm).

The calculation of the triad tacticity is outlined in the techniquesshown in U.S. Pat. No. 5,504,172. Subtraction of the peak areas for theerror in propylene insertions (both 2,1 and 1,3) from peak areas fromthe total peak areas of the second region and the third region, the peakareas based on the 3 propylene units-chains (PPP(mr) and PPP(rr))consisting of head-to-tail bonds can be obtained. Thus, the peak areasof PPP(mm), PPP(mr) and PPP(rr) can be evaluated, and hence the triadtacticity of the propylene unit chain consisting of head-to-tail bondscan be determined.

The polymers of embodiments of the present invention have a triadtacticity of three propylene units, as measured by ¹³C NMR, of 75% orgreater, 80% or greater, 82% or greater, 85% or greater, or 90% orgreater.

In embodiments of the present invention, the polymer has a melt index(MI) of 20 dg/min or less, 7 dg/min or less, 5 dg/min or less, or 2dg/min or less, or less than 2 dg/min. The determination of the MI ofthe polymer is according to ASTM D1238 (190° C., 2.16 kg). In thisversion of the method a portion of the sample extruded during the testwas collected and weighed. This is commonly referred to as themodification 1 of the experimental procedure. The sample analysis isconducted at 190° C. with a 1 minute preheat on the sample to provide asteady temperature for the duration of the experiment.

In one embodiment, the polymer used in the present invention isdescribed in detail as the “Second Polymer Component (SPC)” in WO00/69963, WO 00/01766, WO 99/07788, WO 02/083753, and described infurther detail as the “Propylene Olefin Copolymer” in WO 00/01745, allof which are fully incorporated by reference herein for purposes of U.S.patent practice.

In a preferred embodiment, the NFP is an isoparaffin comprising C₆ toC₂₅ isoparaffins. In another embodiment the non-functionalizedplasticizer is a polyalphaolefin comprising C₁₀ to C₁₀₀ n-paraffins. Thepolyolefin may be a polypropylene homopolymer, copolymer, impactcopolymer, or blends thereof, and may include a plastomer. Non-limitingexamples of desirable articles of manufacture made from compositions ofthe invention include films, sheets, fibers, woven and nonwoven fabrics,tubes, pipes, automotive components, furniture, sporting equipment, foodstorage containers, transparent and semi-transparent articles, toys,tubing and pipes, and medical devices. The compositions of the inventionmay be characterized by having an improved (decreased) T_(g) relative tothe starting polyolefin, while maintaining other desirable properties.

The enhanced properties of the plasticized polyolefin compositionsdescribed herein are useful in a wide variety of applications, includingtransparent articles such as cook and storage ware, and in otherarticles such as furniture, automotive components, toys, sportswear,medical devices, sterilizable medical devices and sterilizationcontainers, nonwoven fibers and fabrics and articles therefrom such asdrapes, gowns, filters, hygiene products, diapers, and films, orientedfilms, sheets, tubes, pipes and other items where softness, high impactstrength, and impact strength below freezing is important. Fabricationof the plasticized polyolefins of the invention to form these articlesmay be accomplished by injection molding, extrusion, thermoforming, blowmolding, rotomolding, spunbonding, meltblowing, fiber spinning, blownfilm, stretching for oriented films, and other common processingmethods.

Preparing the Polyolefin/NFP Blend

The polyolefin suitable for use in the present invention can be in anyphysical form when used to blend with the NFP of the invention. In oneembodiment, reactor granules, defined as the granules of polymer thatare isolated from the polymerization reactor prior to any processingprocedures, are used to blend with the NFP of the invention. The reactorgranules have an average diameter of from 50 μm to 10 mm in oneembodiment, and from 10 μm to 5 mm in another embodiment. In anotherembodiment, the polyolefin is in the form of pellets, such as, forexample, having an average diameter of from 1 mm to 10 mm that areformed from melt extrusion of the reactor granules.

In one embodiment of the invention, the polyolefin suitable for thecomposition excludes physical blends of polypropylene with otherpolyolefins, and in particular, excludes physical blends ofpolypropylene with low molecular weight (500 to 10,000 g/mol)polyethylene or polyethylene copolymers, meaning that, low molecularweight polyethylene or polyethylene copolymers are not purposefullyadded in any amount to the polyolefin (e.g., polypropylene homopolymeror copolymer) compositions of the invention, such as is the case in, forexample, WO 01/18109 A1.

The polyolefin and NFP can be blended by any suitable means, and aretypically blended to obtain a homogeneous, single phase mixture. Forexample, they may be blended in a tumbler, static mixer, batch mixer,extruder, or a combination thereof. The mixing step may take place aspart of a processing method used to fabricate articles, such as in theextruder on an injection molding maching or fiber line.

In one embodiment of compositions of the present invention, conventionalplasticizers such as is commonly used for poly(vinyl chloride) aresubstantially absent. In particular, plasticizers such as phthalates,adipates, trimellitate esters, polyesters, and other functionalizedplasticizers as disclosed in, for example, U.S. Pat. No. 3,318,835; U.S.Pat. No. 4,409,345; WO 02/31044 A1; and PLASTICS ADDITIVES 499-504(Geoffrey Pritchard, ed., Chapman & Hall 1998) are substantially absent.By “substantially absent”, it is meant that these compounds are notadded deliberately to the compositions and if present at all, arepresent at less than 0.5 weight %.

Oils such as naphthenic and other aromatic containing oils arepreferably present to less than 0.5 wt % of the compositions of theinvention in a further embodiment. Also, aromatic moieties andcarbon-carbon unsaturation are substantially absent from thenon-functionalized plasticizers used in the present invention in yetanother embodiment. Aromatic moieties include a compound whose moleculeshave the ring structure characteristic of benzene, naphthalene,phenanthrene, anthracene, etc. By “substantially absent”, it is meantthat these aromatic compounds or moieties are not added deliberately tothe compositions, and if present, are present to less than 0.5 wt % ofthe composition.

In another embodiment of compositions of the present invention,conventional plasticizers, elastomers, or “compatibilizers” such as lowmolecular weight polyethylene are substantially absent. In particular,ethylene homopolymers and copolymers having a weight average molecularweight of from 500 to 10,000 are substantially absent. Such polyethylenecompatibilizers are disclosed in, for example, WO 01/18109 A1. By“substantially absent”, it is meant that these compounds are not addeddeliberately to the compositions and, if present, are present at lessthan 5 weight %, more preferably less than 4 weight %, more preferablyless than 3 weight %, more preferably less than 2 weight %, morepreferably less than 1 weight %, more preferably less than 0.5 weight %,based upon the weight of the polyolefin, the ethylene polymer orcopolymer, and the NFP.

The polyolefin compositions of the present invention may also containother additives. Those additives include adjuvants, oils, plasticizers,block, antiblock, color masterbatches, processing aids, neutralizers,lubricants, waxes, antioxidants, nucleating agents, acid scavengers,stabilizers, surfactants, anticorrosion agents, cavitating agents,blowing agents, other UV absorbers such as chain-breaking antioxidants,etc., quenchers, antistatic agents, slip agents, pigments, dyes, fillersand cure agents such as peroxide. The additives may be present in thetypically effective amounts well known in the art, such as 0.001 weight% to 10 weight %. Preferably, dyes and other colorants common in theindustry may be present from 0.01 to 10 wt % in one embodiment, and from0.1 to 6 wt % in another embodiment. Suitable nucleating agents aredisclosed by, for example, H. N. Beck in Heterogeneous Nucleating Agentsfor Polypropylene Crystallization, 11 J. APPLIED POLY. SCI. 673-685(1967) and in Heterogeneous Nucleation Studies on Polypropylene, 21 J.POLY. SCI.: POLY. LETTERS 347-351 (1983). Examples of suitablenucleating agents are sodium benzoate, sodium2,2′-methylenebis(4,6-di-tert-butylphenyl)phosphate, aluminum2,2′-methylenebis(4,6-di-tert-butylphenyl)phosphate, dibenzylidenesorbitol, di(p-tolylidene) sorbitol, di(p-ethylbenzylidene)sorbitol,bis(3,4-dimethylbenzylidene)sorbitol, andN′,N′-dicyclohexyl-2,6-naphthalenedicarboxamide, and salts ofdisproportionated rosin esters. The foregoing list is intended to beillustrative of suitable choices of nucleating agents for inclusion inthe instant formulations.

In particular, antioxidants and stabilizers such as organic phosphites,hindered amines, and phenolic antioxidants may be present in thepolyolefin compositions of the invention from 0.001 to 2 wt % in oneembodiment, and from 0.01 to 0.8 wt % in another embodiment, and from0.02 to 0.5 wt % in yet another embodiment. Non-limiting examples oforganic phosphites that are suitable aretris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168) anddi(2,4-di-tert-butylphenyl)pentaerithritol diphosphite (ULTRANOX 626).Non-limiting examples of hindered amines includepoly[2-N,N′-di(2,2,6,6-tetramethyl-4-piperidinyl)-hexanediamine-4-(1-amino-1,1,3,3-tetramethylbutane)sym-triazine](CHIMASORB 944); bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (TINUVIN770). Non-limiting examples of phenolic antioxidants includepentaerythrityl tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate(IRGANOX 1010); and1,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX 3114).Preferred antioxidants include phenolic antioxidants, such as Irganox1010, Irganox, 1076 both available from Ciba-Geigy.

Preferred oils include paraffinic or naphthenic oils such as Primol 352,or Primol 876 available from ExxonMobil Chemical France, S.A. in Paris,France. More preferred oils include aliphatic naphthenic oils, whiteoils or the like.

Fillers may be present from 0.1 to 50 wt % in one embodiment, and from0.1 to 25 wt % of the composition in another embodiment, and from 0.2 to10 wt % in yet another embodiment. Desirable fillers include but notlimited to titanium dioxide, silicon carbide, silica (and other oxidesof silica, precipitated or not), antimony oxide, lead carbonate, zincwhite, lithopone, zircon, corundum, spinel, apatite, Barytes powder,barium sulfate, magnesiter, carbon black, dolomite, calcium carbonate,talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr orFe and CO₃ and/or HPO₄, hydrated or not; quartz powder, hydrochloricmagnesium carbonate, glass fibers, clays, alumina, and other metaloxides and carbonates, metal hydroxides, chrome, phosphorous andbrominated flame retardants, antimony trioxide, silica, silicone, andblends thereof. These fillers may particularly include any other fillersand porous fillers and supports known in the art, and may have the NFPof the invention pre-contacted, or pre-absorbed into the filler prior toaddition to the polyolefin in one embodiment.

Preferred fillers, cavitating agents and/or nucleating agents includetitanium dioxide, calcium carbonate, barium sulfate, silica, silicondioxide, carbon black, sand, glass beads, mineral aggregates, talc, clayand the like.

More particularly, in one embodiment of the present invention, the NFP,or some portion of the NFP, may be blended with a filler, desirably aporous filler. The NFP and filler may be blended by, for example, atumbler or other wet blending apparatus. The NFP and filler in thisembodiment are blended for a time suitable to form a homogenouscomposition of NFP and filler, desirably from 1 minute to 5 hours in oneembodiment. This NFP/filler blend may then be blended with thepolyolefin useful in the invention in order to effectuate plasticationof the polyolefin. In another embodiment, a porous filler may becontacted with the NFP, or some portion thereof, prior to contacting thefiller with the polyolefin. In another embodiment, the porous filler,polyolefin and NFP are contacted simultaneously (or in the same blendingapparatus). In any case, the NFP may be present from 0.1 to 60 wt % ofthe composition, and from 0.2 to 40 wt % in another embodiment, and from0.3 to 20 wt % in yet another embodiment.

Fatty acid salts may also be present in the polyolefin compositions ofthe present invention. Such salts may be present from 0.001 to 1 wt % ofthe composition in one embodiment, and from 0.01 to 0.8 wt % in anotherembodiment. Examples of fatty acid metal salts include lauric acid,stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalicacid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenicacid, oleic acid, palmitic acid, and erucic acid, suitable metalsincluding Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and so forth.Preferable fatty acid salts are selected from magnesium stearate,calcium stearate, sodium stearate, zinc stearate, calcium oleate, zincoleate, and magnesium oleate.

In some embodiments the plasticized polyolefins produced by thisinvention may be blended with one or more other polymers, including butnot limited to, thermoplastic polymer(s) and/or elastomer(s).

By “thermoplastic polymer(s)” is meant a polymer that can be melted byheat and then cooled with out appreciable change in properties.Thermoplastic polymers typically include, but are not limited to,polyolefins, polyamides, polyesters, polycarbonates, polysulfones,polyacetals, polylactones, acrylonitrile-butadiene-styrene resins,polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrileresins, styrene maleic anhydride, polyimides, aromatic polyketones, ormixtures of two or more of the above. Preferred polyolefins include, butare not limited to, polymers comprising one or more linear, branched orcyclic C₂ to C₄₀ olefins, preferably polymers comprising propylenecopolymerized with one or more C₃ to C₄₀ olefins, preferably a C₃ to C₂₀alpha olefin, more preferably C₃ to C₁₀ alpha-olefins. More preferredpolyolefins include, but are not limited to, polymers comprisingethylene including but not limited to ethylene copolymerized with a C₃to C₄₀ olefin, preferably a C₃ to C₂₀ alpha olefin, more preferablypropylene and or butene.

By elastomers is meant all natural and synthetic rubbers, includingthose defined in ASTM D1566. Examples of preferred elastomers include,but are not limited to, ethylene propylene rubber, ethylene propylenediene monomer rubber, styrenic block copolymer rubbers (including SI,SIS, SB, SBS, SIBS and the like, where S=styrene, I=isobutylene, andB=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutyleneand para-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene, natural rubber, polyisoprene, copolymers of butadienewith acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinatedisoprene rubber, acrylonitrile chlorinated isoprene rubber,polybutadiene rubber (both cis and trans).

In another embodiment, the blend comprising the NFP may further becombined with one or more of polybutene, ethylene vinyl acetate, lowdensity polyethylene (density 0.915 to less than 0.935 g/cm³) linear lowdensity polyethylene, ultra low density polyethylene (density 0.86 toless than 0.90 g/cm³), very low density polyethylene (density 0.90 toless than 0.915 g/cm³), medium density polyethylene (density 0.935 toless than 0.945 g/cm³), high density polyethylene (density 0.945 to 0.98g/cm³), ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, crosslinkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols and/or polyisobutylene.Preferred polymers include those available from Exxon Chemical Companyin Baytown, Tex. under the tradenames EXCEED™ and EXACT™.

In another embodiment, tackifiers may be blended with the plasticizedpolyolefins of this invention. Examples of useful tackifiers include,but are not limited to, aliphatic hydrocarbon resins, aromatic modifiedaliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins,polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins,wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes,aromatic modified polyterpenes, terpene phenolics, aromatic modifiedhydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin,hydrogenated aliphatic aromatic resins, hydrogenated terpenes andmodified terpenes, and hydrogenated rosin esters. In some embodimentsthe tackifier is hydrogenated. In other embodiments the tackifier isnon-polar. (Non-polar meaning that the tackifier is substantially freeof monomers having polar groups. Preferably the polar groups are notpresent, however if they are preferably they are not present at morethat 5 weight %, preferably not more that 2 weight %, even morepreferably no more than 0.5 weight %.) In some embodiments the tackifierhas a softening point (Ring and Ball, as measured by ASTM E-28) of 80°C. to 140° C., preferably 100° C. to 130° C. The tackifier, if present,is typically present at about 1 weight % to about 50 weight %, basedupon the weight of the blend, more preferably 10 weight % to 40 weight%, even more preferably 20 weight % to 40 weight %. Preferably however,tackifier is not present, or if present, is present at less than 10weight %, preferably less than 5 weight %, more preferably at less than1 weight %.

More particularly, the components of the polyolefinic composition of thepresent invention may be blended by any suitable means to form theplasticized polyolefin, which is then suitable for further processinginto useful articles. In one aspect of the invention, the polyolefin andNFP are blended, or melt blended, in an apparatus such as an extruder orbatch mixer. The polyolefin may also be blended with the NFP using atumbler, double-cone blender, ribbon blender, or other suitable blender.In yet another embodiment, the polyolefin and NFP are blended by acombination of, for example, a tumbler, followed by melt blending in anextruder. Extrusion technology for polypropylene is described in moredetail in, for example, PLASTICS EXTRUSION TECHNOLOGY 26-37 (FriedhelmHensen, ed. Hanser Publishers 1988) and in POLYPROPYLENE HANDBOOK304-348 (Edward P. Moore, Jr. ed., Hanser Publishers 1996).

More particularly, the components of the polyolefinic composition of thepresent invention may be blended in solution by any suitable means toform the plasticized polyolefin, by using a solvent that dissolves bothcomponents to a significant extent. The blending may occur at anytemperature or pressure where the NFP and the polyolefin remain insolution. Preferred conditions include blending at high temperatures,such as 20° C. or more, preferably 40° C. or more over the melting pointof the polyolefin. For example iPP would typically be solution blendedwith the NFP at a temperature of 200° C. or more, preferably 220° C. ormore. Such solution blending would be particularly useful in processeswhere the polyolefin is made by solution process and the NFP is addeddirectly to the finishing train, rather than added to the dry polymer inanother blending step altogether. Such solution blending would also beparticularly useful in processes where the polyolefin is made in a bulkor high pressure process where the both the polymer and the NFP weresoluble in the monomer. As with the solution process the NFP is addeddirectly to the finishing train, rather than added to the dry polymer inanother blending step altogether.

The polyolefin suitable for use in the present invention can be in anyphysical form when used to blend with the NFP of the invention. In oneembodiment, reactor granules, defined as the granules of polymer thatare isolated from the polymerization reactor, are used to blend with theNFP of the invention. The reactor granules have an average diameter offrom 10 μm to 5 mm, and from 50 μm to 10 mm in another embodiment.Alternately, the polyolefin is in the form of pellets, such as, forexample, having an average diameter of from 1 mm to 6 mm that are formedfrom melt extrusion of the reactor granules.

One method of blending the NFP with the polyolefin is to contact thecomponents in a tumbler, the polyolefin being in the form of reactorgranules. This works particularly well with polypropylene homopolymerand random copolymer. This can then be followed, if desired, by meltblending in an extruder. Another method of blending the components is tomelt blend the polyolefin pellets with the NFP directly in an extruderor batch mixer, such as a Brabender mixer.

Thus, in the cases of injection molding of various articles, simplesolid state blends of the pellets serve equally as well as pelletizedmelt state blends of raw polymer granules, of granules with pellets, orof pellets of the two components since the forming process includes aremelting and mixing of the raw material. In the process of compressionmolding of medical devices, however, little mixing of the meltcomponents occurs, and a pelletized melt blend would be preferred oversimple solid state blends of the constituent pellets and/or granules.Those skilled in the art will be able to determine the appropriateprocedure for blending of the polymers to balance the need for intimatemixing of the component ingredients with the desire for process economy.

Applications

The resultant plasticized polyolefin of the present invention may beprocessed by any suitable means such as by calendering, casting,coating, compounding, extrusion, foamed, laminated, blow molding,compression molding, injection molding, thermoforming, transfer molding,cast molding, rotational molding, casting such as for films, spun ormelt bonded such as for fibers, or other forms of processing such asdescribed in, for example, PLASTICS PROCESSING (Radian Corporation,Noyes Data Corp. 1986). More particularly, with respect to the physicalprocess of producing the blend, sufficient mixing should take place toassure that a uniform blend will be produced prior to conversion into afinished product.

The compositions of this invention (and blends thereof as describedabove) may be used in any known thermoplastic or elastomer application.Examples include uses in molded parts, films, tapes, sheets, tubing,hose, sheeting, wire and cable coating, adhesives, shoesoles, bumpers,gaskets, bellows, films, fibers, elastic fibers, nonwovens, spunbonds,sealants, surgical gowns and medical devices.

These devices may be made or formed by any useful forming means forforming polyolefins. This will include, at least, molding includingcompression molding, injection molding, blow molding, and transfermolding; film blowing or casting; extrusion, and thermoforming; as wellas by lamination, pultrusion, protrusion, draw reduction, rotationalmolding, spinbonding, melt spinning, melt blowing; or combinationsthereof. Use of at least thermoforming or film applications allows forthe possibility of and derivation of benefits from uniaxial or biaxialorientation of the radiation tolerant material.

Adhesives

The polymers of this invention or blends thereof can be used asradiation resistant adhesives, either alone or combined with tackifiers.Preferred tackifiers are described above. The tackifier is typicallypresent at about 1 weight % to about 50 weight %, based upon the weightof the blend, more preferably 10 weight % to 40 weight %, even morepreferably 20 weight % to 40 weight %. Other additives, as describedabove, may be added also.

The radiation resistant adhesives of this invention can be used in anyadhesive application, including but not limited to, disposables,packaging, laminates, pressure sensitive adhesives, tapes labels, woodbinding, paper binding, non-wovens, road marking, reflective coatings,and the like. In a preferred embodiment the adhesives of this inventioncan be used for disposable diaper and napkin chassis construction,elastic attachment in disposable goods converting, packaging, labeling,bookbinding, woodworking, and other assembly applications. Particularlypreferred applications include: baby diaper leg elastic, diaper frontaltape, diaper standing leg cuff, diaper chassis construction, diaper corestabilization, diaper liquid transfer layer, diaper outer coverlamination, diaper elastic cuff lamination, feminine napkin corestabilization, feminine napkin adhesive strip, industrial filtrationbonding, industrial filter material lamination, filter mask lamination,surgical gown lamination, surgical drape lamination, and perishableproducts packaging.

Films

Polyolefin films are widely used; for example, in shopping bags,pressure sensitive tape, gift wrap, labels, food packaging, etc. Most ofthese applications require high tear (in machine and transversedirections) and impact strengths, puncture resistance, high gloss, andlow haziness.

The compositions described above and the blends thereof may be formedinto monolayer or multilayer films appropriate for such applications.These films may be formed by any of the conventional techniques known inthe art including extrusion, co-extrusion, extrusion coating,lamination, blowing and casting. The film may be obtained by the flatfilm or tubular process which may be followed by orientation in anuniaxial direction or in two mutually perpendicular directions in theplane of the film. One or more of the layers of the film may be orientedin the transverse and/or longitudinal directions to the same ordifferent extents. This orientation may occur before or after theindividual layers are brought together. For example a polyethylene layercan be extrusion coated or laminated onto an oriented polypropylenelayer or the polyethylene and polypropylene can be coextruded togetherinto a film then oriented. Likewise, oriented polypropylene could belaminated to oriented polyethylene or oriented polyethylene could becoated onto polypropylene then optionally the combination could beoriented even further. Typically the films are oriented in the MachineDirection (MD) at a ratio of up to 15, preferably between 5 and 7, andin the Transverse Direction (TD) at a ratio of up to 15 preferably 7 to9. However in another embodiment the film is oriented to the same extentin both the MD and TD directions.

In another embodiment the layer comprising the plasticized polyolefincomposition of this invention (and/or blends thereof) may be combinedwith one or more other layers. The other layer(s) may be any layertypically included in multilayer film structures. For example the otherlayer or layers may be:

1. Polyolefins

-   -   Preferred polyolefins include homopolymers or copolymers of C₂        to C₄₀ olefins, preferably C₂ to C₂₀ olefins, preferably a        copolymer of an alpha-olefin and another olefin or alpha-olefin        (ethylene is defined to be an alpha-olefin for purposes of this        invention). Preferably homopolyethylene, homopolypropylene,        propylene copolymerized with ethylene and or butene, ethylene        copolymerized with one or more of propylene, butene or hexene,        and optional dienes. Preferred examples include thermoplastic        polymers such as ultra low density polyethylene, very low        density polyethylene, linear low density polyethylene, low        density polyethylene, medium density polyethylene, high density        polyethylene, polypropylene, isotactic polypropylene, highly        isotactic polypropylene, syndiotactic polypropylene, random        copolymer of propylene and ethylene and/or butene and/or hexene,        elastomers such as ethylene propylene rubber, ethylene propylene        diene monomer rubber, neoprene, and blends of thermoplastic        polymers and elastomers, such as for example, thermoplastic        elastomers and rubber toughened plastics.

2. Polar Polymers

-   -   Preferred polar polymers include homopolymers and copolymers of        esters, amides, actates, anhydrides, copolymers of a C₂ to C₂₀        olefin, such as ethylene and/or propylene and/or butene with one        or more polar monomers such as acetates, anhydrides, esters,        alcohol, and or acrylics. Preferred examples include polyesters,        polyamides, ethylene vinyl acetate copolymers, and polyvinyl        chloride.        3. Cationic polymers Preferred cationic polymers include        polymers or copolymers of geminally disubstituted olefins,        alpha-heteroatom olefins and/or styrenic monomers. Preferred        geminally disubstituted olefins include isobutylene, isopentene,        isoheptene, isohexane, isooctene, isodecene, and isododecene.        Preferred alpha-heteroatom olefins include vinyl ether and vinyl        carbazole, preferred styrenic monomers include styrene, alkyl        styrene, para-alkyl styrene, alpha-methyl styrene,        chloro-styrene, and bromo-para-methyl styrene. Preferred        examples of cationic polymers include butyl rubber, isobutylene        copolymerized with para methyl styrene, polystyrene, and        poly-alpha-methyl styrene.

4. Miscellaneous

-   -   Other preferred layers can be paper, wood, cardboard, metal,        metal foils (such as aluminum foil and tin foil), metallized        surfaces, glass (including silicon oxide (SiO.x) coatings        applied by evaporating silicon oxide onto a film surface),        fabric, spunbonded fibers, and non-wovens (particularly        polypropylene spun bonded fibers or non-wovens), and substrates        coated with inks, dyes, pigments, and the like.

The films may vary in thickness depending on the intended application,however films of a thickness from 1 to 250 μm are usually suitable.Films intended for packaging are usually from 10 to 60 micron thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

Additives such as block, antiblock, antioxidants, pigments, fillers,processing aids, UV stabilizers, neutralizers, lubricants, surfactantsand/or nucleating agents may also be present in one or more than onelayer in the films. Preferred additives include silicon dioxide,titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calciumsterate, carbon black, low molecular weight resins and glass beads.

In another embodiment one more layers may be modified by coronatreatment, electron beam irradiation, gamma irradiation, or microwaveirradiation. In a preferred embodiment one or both of the surface layersis modified by corona treatment.

The films described herein may also comprise from 5 to 60 weight %,based upon the weight of the polymer and the resin, of a hydrocarbonresin. The resin may be combined with the polymer of the seal layer(s)or may be combined with the polymer in the core layer(s). The resinpreferably has a softening point above 100° C., even more preferablyfrom 130 to 180° C. Preferred hydrocarbon resins include those describedabove. The films comprising a hydrocarbon resin may be oriented inuniaxial or biaxial directions to the same or different degrees.

Molded Products

The plasticized polyolefin composition described above may also be usedto prepare molded products in any molding process, including but notlimited to, injection molding, gas-assisted injection molding, extrusionblow molding, injection blow molding, injection stretch blow molding,compression molding, rotational molding, foam molding, thermoforming,sheet extrusion, and profile extrusion. The molding processes are wellknown to those of ordinary skill in the art.

The compositions described herein may be shaped into desirable end usearticles by any suitable means known in the art. Thermoforming, vacuumforming, blow molding, rotational molding, slush molding, transfermolding, wet lay-up or contact molding, cast molding, cold formingmatched-die molding, injection molding, spray techniques, profileco-extrusion, or combinations thereof are typically used methods.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. An embodiment of a thermoforming sequence isdescribed, however this should not be construed as limiting thethermoforming methods useful with the compositions of this invention.First, an extrudate film of the composition of this invention (and anyother layers or materials) is placed on a shuttle rack to hold it duringheating. The shuttle rack indexes into the oven which pre-heats the filmbefore forming. Once the film is heated, the shuttle rack indexes backto the forming tool. The film is then vacuumed onto the forming tool tohold it in place and the forming tool is closed. The forming tool can beeither “male” or “female” type tools. The tool stays closed to cool thefilm and the tool is then opened. The shaped laminate is then removedfrom the tool.

Thermoforming is accomplished by vacuum, positive air pressure,plug-assisted vacuum forming, or combinations and variations of these,once the sheet of material reaches thermoforming temperatures, typicallyof from 140° C. to 185° C. or higher. A pre-stretched bubble step isused, especially on large parts, to improve material distribution. Inone embodiment, an articulating rack lifts the heated laminate towards amale forming tool, assisted by the application of a vacuum from orificesin the male forming tool. Once the laminate is firmly formed about themale forming tool, the thermoformed shaped laminate is then cooled,typically by blowers. Plug-assisted forming is generally used for small,deep drawn parts. Plug material, design, and timing can be critical tooptimization of the process. Plugs made from insulating foam avoidpremature quenching of the plastic. The plug shape is usually similar tothe mold cavity, but smaller and without part detail. A round plugbottom will usually promote even material distribution and uniformside-wall thickness. For a semicrystalline polymer such aspolypropylene, fast plug speeds generally provide the best materialdistribution in the part.

The shaped laminate is then cooled in the mold. Sufficient cooling tomaintain a mold temperature of 30° C. to 65° C. is desirable. The partis below 90° C. to 100° C. before ejection in one embodiment. For thegood behavior in thermoforming, the lowest melt flow rate polymers aredesirable. The shaped laminate is then trimmed of excess laminatematerial.

Blow molding is another suitable forming means, which includes injectionblow molding, multi-layer blow molding, extrusion blow molding, andstretch blow molding, and is especially suitable for substantiallyclosed or hollow objects, such as, for example, gas tanks and otherfluid containers. Blow molding is described in more detail in, forexample, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92(Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).

In yet another embodiment of the formation and shaping process, profileco-extrusion can be used. The profile co-extrusion process parametersare as above for the blow molding process, except the die temperatures(dual zone top and bottom) range from 150° C.-235° C., the feed blocksare from 90° C.-250° C., and the water cooling tank temperatures arefrom 10° C.-40° C.

One embodiment of an injection molding process is described as follows.The shaped laminate is placed into the injection molding tool. The moldis closed and the substrate material is injected into the mold. Thesubstrate material has a melt temperature between 200° C. and 300° C. inone embodiment, and from 215° C. and 250° C. and is injected into themold at an injection speed of between 2 and 10 seconds. After injection,the material is packed or held at a predetermined time and pressure tomake the part dimensionally and aesthetically correct. Typical timeperiods are from 5 to 25 seconds and pressures from 1,380 kPa to 10,400kPa. The mold is cooled between 10° C. and 70° C. to cool the substrate.The temperature will depend on the desired gloss and appearance desired.Typical cooling time is from 10 to 30 seconds, depending on part on thethickness. Finally, the mold is opened and the shaped composite articleejected.

Likewise, molded articles may be fabricated by injecting molten polymerinto a mold that shapes and solidifies the molten polymer into desirablegeometry and thickness of molded articles. Sheet may be made either byextruding a substantially flat profile from a die, onto a chill roll, oralternatively by calendaring. Sheet will generally be considered to havea thickness of from 10 mils to 100 mils (254 μm to 2540 μm), althoughsheet may be substantially thicker. Tubing or pipe may be obtained byprofile extrusion for uses in medical, potable water, land drainageapplications or the like. The profile extrusion process involves theextrusion of molten polymer through a die. The extruded tubing or pipeis then solidified by chill water or cooling air into a continuousextruded articles. The tubing will generally be in the range of from0.31 cm to 2.54 cm in outside diameter, and have a wall thickness of inthe range of from 254 μm to 0.5 cm. The pipe will generally be in therange of from 2.54 cm to 254 cm in outside diameter, and have a wallthickness of in the range of from 0.5 cm to 15 cm. Sheet made from theproducts of an embodiment of a version of the present invention may beused to form containers. Such containers may be formed by thermoforming,solid phase pressure forming, stamping and other shaping techniques.Sheets may also be formed to cover floors or walls or other surfaces.

In an embodiment of the thermoforming process, the oven temperature isbetween 160° C. and 195° C., the time in the oven between 10 and 20seconds, and the die temperature, typically a male die, between 10° C.and 71° C. The final thickness of the cooled (room temperature), shapedlaminate is from 10 μm to 6000 μm in one embodiment, from 200 μm to 6000μm in another embodiment, and from 250 μm to 3000 μm in yet anotherembodiment, and from 500 μm to 1550 μm in yet another embodiment, adesirable range being any combination of any upper thickness limit withany lower thickness limit.

In an embodiment of the injection molding process, wherein a substratematerial in injection molded into a tool including the shaped laminate,the melt temperature of the substrate material is between 230° C. and255° C. in one embodiment, and between 235° C. and 250° C. in anotherembodiment, the fill time from 2 to 10 seconds in one embodiment, from 2to 8 seconds in another embodiment, and a tool temperature of from 25°C. to 65° C. in one embodiment, and from 27° C. and 60° C. in anotherembodiment. In a desirable embodiment, the substrate material is at atemperature that is hot enough to melt any tie-layer material or backinglayer to achieve adhesion between the layers.

In yet another embodiment of the invention, the compositions of thisinvention may be secured to a substrate material using a blow moldingoperation. Blow molding is particularly useful in such applications asfor making closed articles such as fuel tanks and other fluidcontainers, playground equipment, outdoor furniture and small enclosedstructures. In one embodiment of this process, Compositions of thisinvention are extruded through a multi-layer head, followed by placementof the uncooled laminate into a parison in the mold. The mold, witheither male or female patterns inside, is then closed and air is blowninto the mold to form the part.

It will be understood by those skilled in the art that the stepsoutlined above may be varied, depending upon the desired result. Forexample, the an extruded sheet of the compositions of this invention maybe directly thermoformed or blow molded without cooling, thus skipping acooling step. Other parameters may be varied as well in order to achievea finished composite article having desirable features.

Preferred articles made using the plasticized polyolefins of thisInvention include cookware, storageware, toys, medical devices,sterilizable medical devices, sterilization containers, healthcareitems, sheets, crates, containers, bottles, packaging, wire and cablejacketing, pipes, geomembranes, sporting equipment, chair mats, tubing,profiles, instrumentation sample holders and sample windows, outdoorfurniture (e.g., garden furniture), playground equipment, automotive,boat and water craft components, and other such articles. In particular,the compositions are suitable for automotive components such as bumpers,grills, trim parts, dashboards and instrument panels, exterior door andhood components, spoiler, wind screen, hub caps, mirror housing, bodypanel, protective side molding, and other interior and externalcomponents associated with automobiles, trucks, boats, and othervehicles.

Test Methods Dynamic Mechanical Thermal Analysis

The glass transition temperature (T_(g)) and storage modulus (E′) weremeasured using dynamic mechanical thermal analysis (DMTA). This testprovides information about the small-strain mechanical response(relaxation behavior) of a sample as a function of temperature over atemperature range that includes the glass transition region and thevisco-elastic region prior to melting.

Typically, samples were tested using a three point bending configuration(TA Instruments DMA 2980). A solid rectangular compression molded barwas placed on two fixed supports; a movable clamp applied a periodicdeformation to the sample midpoint at a frequency of 1 Hz and anamplitude of 20 μm. The sample was initially cooled to −130° C. thenheated to 60° C. at a heating rate of 3° C./min. In some cases,compression molded bars were tested using other deformationconfigurations, namely dual cantilever bending and tensile elongation(Rheometrics RSAII). The periodic deformation under these configurationswas applied at a frequency of 1 Hz and strain amplitude of 0.05%. Thesample was cooled to −130° C. and then heated to 60° C. at a rate of 2°C./min. The slightly difference in heating rate does not influence theglass transition temperature measurements significantly.

The output of these DMTA experiments is the storage modulus (E′) andloss modulus (E″). The storage modulus measures the elastic response orthe ability of the material to store energy, and the loss modulusmeasures the viscous response or the ability of the material todissipate energy. Tan δ is the ratio of E″/E′ and gives a measure of thedamping ability of the material. The beginning of the broad glasstransition (β-relaxation) is identified as the extrapolated tangent tothe Tan δ peak. In addition, the peak temperature and area under thepeak are also measured to more fully characterize the transition fromglassy to visco-elastic region.

Differential Scanning Calorimetry

Crystallization temperature (T_(c)) and melting temperature (T_(m)) weremeasured using Differential Scanning Calorimetry (DSC). This analysiswas conducted using either a TA Instruments MDSC 2920 or a Perkin ElmerDSC7. Typically, 6 to 10 mg of molded polymer or plasticized polymer wassealed in an aluminum pan and loaded into the instrument at roomtemperature. Melting data (first heat) were acquired by heating thesample to at least 30° C. above its melting temperature at a heatingrate of 10° C./min. This provides information on the melting behaviorunder as-molded conditions, which can be influenced by thermal historyas well as any molded-in orientation or stresses. The sample was thenheld for 10 minutes at this temperature to destroy its thermal history.Crystallization data was acquired by cooling the sample from the melt toat least 50° C. below the crystallization temperature at a cooling rateof 10° C./min. The sample was then held at 25° C. for 10 minutes, andfinally heated at 10° C./min to acquire additional melting data (secondheat). This provides information about the melting behavior after acontrolled thermal history and free from potential molded-in orientationand stress effects. The endothermic melting transition (first and secondheat) and exothermic crystallization transition were analyzed for onsetof transition and peak temperature. The melting temperatures reported inthe tables are the peak melting temperatures from the second heat unlessotherwise indicated. For polymers displaying multiple peaks, the highermelting peak temperature is reported.

Areas under the curve was used to determine the heat of fusion (ΔH_(f))which can be used to calculate the degree of crystallinity. A value of207 J/g was used as the equilibrium heat of fusion for 100% crystallinepolypropylene (obtained from B. Wunderlich, “Thermal Analysis”, AcademicPress, Page 418, 1990). The percent crystallinity is calculated usingthe formula, [area under the curve (J/g)/207 (J/g)]*100.

Size-Exclusion Chromatography of Polymers

Molecular weight distribution was characterized using Size-ExclusionChromatography (SEC). Molecular weight (weight-average molecular weight,Mw, and number-average molecular weight, Mn) were determined using aHigh Temperature Size Exclusion Chromatograph (either from WatersCorporation or Polymer Laboratories), equipped with a differentialrefractive index detector (DRI), an online light scattering detector,and a viscometer. Experimental details not described below, includinghow the detectors were calibrated, are described in: T. Sun, P. Brant,R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001).

Three Polymer Laboratories PLgel 10 mm Mixed-B columns were used. Thenominal flow rate was 0.5 cm³/min, and the nominal injection volume was300 μL. The various transfer lines, columns and differentialrefractometer (the DRI detector) were contained in an oven maintained at135° C.

Solvent for the SEC experiment was prepared by dissolving 6 grams ofbutylated hydroxy toluene as an antioxidant in 4 liters of Aldrichreagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture was thenfiltered through a 0.7 μm glass pre-filter and subsequently through a0.1 μm Teflon filter. The TCB was then degassed with an online degasserbefore entering the SEC.

Polymer solutions were prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities weremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/ml at room temperatureand 1.324 g/ml at 135° C. The injection concentration ranged from 1.0 to2.0 mg/ml, with lower concentrations being used for higher molecularweight samples.

Prior to running each sample the DRI detector and the injector werepurged. Flow rate in the apparatus was then increased to 0.5 ml/minute,and the DRI was allowed to stabilize for 8-9 hours before injecting thefirst sample. The LS laser was turned on 1 to 1.5 hours before runningsamples.

The concentration, c, at each point in the chromatogram is calculatedfrom the baseline-subtracted DRI signal, I_(DRI), using the followingequation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the same as described below for the LS analysis. Units onparameters throughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The light scattering detector used was a Wyatt Technology HighTemperature mini-DAWN. The polymer molecular weight, M, at each point inthe chromatogram is determined by analyzing the LS output using the Zimmmodel for static light scattering (M. B. Huglin, LIGHT SCATTERING FROMPOLYMER SOLUTIONS, Academic Press, 1971):

$\frac{K_{o}c}{\Delta \; {R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{c}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient, P(θ) is the formfactor for a monodisperse random coil (described in the abovereference), and K_(o) is the optical constant for the system:

$K_{o} = \frac{4\pi^{2}{n^{2}\left( {{n}/{c}} \right)}^{2}}{\lambda^{4}N_{A}}$

in which N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 135°C. and λ=690 nm. In addition, A₂=0.0006 for propylene polymers and0.0015 for butene polymers, and (dn/dc)=0.104 for propylene polymers and0.098 for butene polymers.

A high temperature Viscotek Corporation viscometer was used, which hasfour capillaries arranged in a Wheatstone bridge configuration with twopressure transducers. One transducer measures the total pressure dropacross the detector, and the other, positioned between the two sides ofthe bridge, measures a differential pressure. The specific viscosity,η_(s), for the solution flowing through the viscometer is calculatedfrom their outputs. The intrinsic viscosity, [η], at each point in thechromatogram is calculated from the following equation:

η_(s) =c[η]+0.3(c[η])²

where c was determined from the DRI output.

The branching index (g′) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromotographic slices, i, between theintegration limits. The branching index g′ is defined as:

$g^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

where k=0.0002288 and α=0.705 for propylene polymers, and k=0.00018 andα=0.7 for butene polymers. M_(v) is the viscosity-average molecularweight based on molecular weights determined by LS analysis.

¹³C-NMR Spectroscopy

Polymer microstructure was determined by ¹³C-NMR spectroscopy, includingthe concentration of isotactic and syndiotactic diads ([m] and [r]),triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). Samples weredissolved in d₂-1,1,2,2-tetrachloroethane. Spectra were recorded at 125°C. using a NMR spectrometer of 75 or 100 MHz. Polymer resonance peaksare referenced to mmmm=21.8 ppm. Calculations involved in thecharacterization of polymers by NMR follow the work of F. A. Bovey in“Polymer Conformation and Configuration” Academic Press, New York 1969and J. Randall in “Polymer Sequence Determination, ¹³C-NMR Method”,Academic Press, New York, 1977. The percent of methylene sequences oftwo in length, % (CH₂)₂, were calculated as follows: the integral of themethyl carbons between 14-18 ppm (which are equivalent in concentrationto the number of methylenes in sequences of two in length) divided bythe sum of the integral of the methylene sequences of one in lengthbetween 45-49 ppm and the integral of the methyl carbons between 14-18ppm, times 100. This is a minimum calculation for the amount ofmethylene groups contained in a sequence of two or more since methylenesequences of greater than two have been excluded. Assignments were basedon H. N. Cheng and J. A. Ewen, Makromol. Chem. 1989, 190, 1931.

Viscosity of Polymers and Blends

The shear viscosity as a function of shear rate was determined using adual-barrel capillary rheometer. The capillary rheometer (Rosand ModelRAH7/2 by Bohun Instruments) was equipped with a 30:1 length to diameterratio capillary. A total mass of 25-30 g of pellets were packed into thecapillary barrels and preheated at 230° C. for 10 minutes to remove anyentrained air before the test. Each test was performed at 230° C. overthe shear rate range of from 30 to 3000 s⁻¹. Corrections to the data forentrance pressure losses (i.e., the Bagley correction) were performedon-line via simultaneous pressure loss measurements for the flow of thematerial through an orifice that was installed into the second barrel ofthe rheometer.

The dynamic shear viscosity as a function of frequency was determined bysmall-amplitude oscillatory shear rheology. A Rheometrics ScientificDSR-500 dynamic stress-controlled rheometer with a cone and plate samplefixture was used. Testing was performed at 190° C. Samples weresubjected to an oscillatory shear stress at a nominal amplitude of 100Pa by oscillating the upper cone at a fixed frequency, and the resultantstrain was measured. The auto-stress adjustment capability was utilizedto keep the strain within limits of 1-30% (stress adjustment setting=32%of current stress, maximum stress=100 Pa). These conditions ensure thateach material was characterized within its linear viscoelastic region.The dynamic shear viscosity was calculated from the measured strain andapplied stress as a function of frequency. Frequency sweeps wereconducted starting at 500 rad/s and decreasing to 0.02 rad/s, using alogarithmic sweep mode with 6 points per decade.

The dynamic shear viscosity (η*) versus frequency (ω) curves were fittedusing the Cross model (as described in C. W. Macoskco, “Rheology:Principles, Measurements, and Applications”, Wiley-VCH, 1994):

$\eta^{*} = \frac{\eta_{0}}{1 + ({\lambda\omega})^{1 - n}}$

The three parameters in this model are: η₀, the zero-shear viscosity; λ,the average relaxation time; and n, the power law exponent. Thezero-shear viscosity is the value at a plateau in the Newtonian regionof the flow curve at a low frequency, where the dynamic shear viscosityis independent of frequency. The average relaxation time corresponds tothe inverse of the frequency at which shear-thinning starts. The powerlaw exponent n is the slope of the shear thinning region at high shearrates in a log-log plot of dynamic shear viscosity versus frequency.These parameters provide a means to compare the effect of plasticizationon a material's flow behavior, sensitivity to shear, and molecularstructure.

Melt Flow Rate

Melt Flow Rate (MFR) is measured according to ASTM D1238 at 230° C.under a load of 2.16 kg unless otherwise noted. Melt Index (MI) ismeasured according to ASTM D 1238 at 190° C. under a load of 2.16 kg.The units for MFR and MI are g/10 min, or dg/min.

Polymer Density

Density is measured by density-gradient column, such as described inASTM D1505, on a compression-molded specimen that has been slowly cooledto room temperature.

Mechanical Properties

Test specimens for mechanical property testing were injection-molded,unless otherwise specified. The testing temperature was standardlaboratory temperature (23±2° C.) as specified in ASTM D618, unlessotherwise specified. Instron load frames were used for tensile andflexure testing.

Tensile properties were determined according to ASTM D638, includingYoung's modulus (also called modulus of elasticity), yield stress (alsocalled tensile strength at yield), yield strain (also called elongationat yield), break stress (also called tensile strength at break), andbreak strain (also called elongation at break). The energy to yield isdefined as the area under the stress-strain curve from zero strain tothe yield strain. The energy to break is defined as the area under thestress-strain from zero strain to the break strain. Injection-moldedtensile bars were of either ASTM D638 Type I or Type IV geometry, testedat a speed of 2 inch/min. Compression-molded tensile bars were of ASTMD412 Type C geometry, tested at a speed of 20 inch/min. Forcompression-molded specimens only: the yield stress and yield strainwere determined as the 10% offset values as defined in ASTM D638. Breakproperties were reported only if a majority of test specimens brokebefore a strain of about 2000%, which is the maximum strain possible onthe load frame used for testing.

Flexure properties were determined according to ASTM D790A, includingthe 1% secant modulus and 2% secant modulus. In some cases, testspecimen geometry was as specified under the ASTM D790 section “MoldingMaterials (Thermoplastics and Thermosets)”, and the support span was 2inches.

Heat deflection temperature was determined according to ASTM D648, at 66psi, on injection-molded specimens.

Rockwell hardness was determined according to ASTM D785, using theR-scale.

Impact Properties

Gardner impact strength was determined according to ASTM D5420, on 3.5inch diameter×0.125 inch thick injection-molded disks, at the specifiedtemperature.

Notched izod impact resistance was determined according to ASTM D256, atthe specified temperature. A TMI Izod Impact Tester was used. Specimenswere either cut individually from the center portion of injection-moldedASTM D638 Type I tensile bars, or pairs of specimens were made bycutting injection-molded flexure bars in half, where the flexure bargeometry was as specified in the ASTM D790 section “Molding Materials(Thermoplastics and Thermosets)”. The notch was oriented such that theimpact occurred on the notched side of the specimen (following ProcedureA of ASTM D256) in most cases; where specified, the notch orientationwas reversed (following Procedure E of ASTM D256) and referred to as“Reverse Notched Izod” (RNI) or “Unnotched Izod” (UNI) impact. Allspecimens were assigned a thickness of 0.122 inch for calculation of theimpact resistance. All breaks were complete, unless specified otherwise.

Optical Properties

Haze was determined by ASTM D1003, on a 0.04 inch think injection-moldedplaque. Gloss was determined by ASTM D2457, at an angle of 45°.

Fabric and Film Properties

Flexure and tensile properties (including 1% Secant Flexure Modulus,Peak Load, Tensile Strength at Break, and Elongation at Break) aredetermined by ASTM D 882. Elmendorf tear is determined by ASTM D 1922.Puncture and puncture energy are determined by ASTM D 3420. Total energydart impact is determined by ASTM D 4272

Softness or “hand” of spunbond nonwoven fabric as it is known in the artwas measured using the Thwing-Albert Handle-O-Meter (Model211-10-B/America.) The quality of “hand” is considered to be thecombination of resistance due to the surface friction and flexibility ofa fabric material. The Handle-O-Meter measures the above two factorsusing and LVDT (Linear Variable Differential Transformer) to detect theresistance that a blade encounters when forcing a specimen of materialinto a slot of parallel edges. A 3½ digit digital voltmeter (DVM)indicates the resistance directly in grams. The “total hand” of anygiven sheet of material is the average of four readings taken on bothsides and both directions of a test sample and is recorded in grams perstandard width of sample material. A decrease in “total hand” indicatesthe improvement of fabric softness.

Sheet Properties

Optical properties were measured as an average of three positions on thesheet. Haze and clarity were measured in accordance with ASTM D1003.Gloss was measured in accordance with ASTM D523. Flexural modulus wastested along the machine direction of sheet samples using a tensiletester in accordance with ASTM D790. Gardner impact was tested accordingto ASTM D3029-90.

Fluid Properties

Pour Point is measured by ASTM D 97. Kinematic Viscosity (KV) ismeasured by ASTM D 445. Specific gravity is typically determined by ASTMD 4052, at the temperature specified. Viscosity index (VI) is determinedby ASTM D 2270. Boiling point and distillation range are typicallydetermined by ASTM D 86 or ASTM D 1160. Saturates and aromatics contentcan be determined by various methods, such as ASTM D 3238.

The number-average molecular weight (Mn) can be determined by GasChromatography (GC), as described in “Modern Practice of GasChromatography”, R. L. Grob and E. F. Barry, Wiley-Interscience, 3rdEdition (July 1995); or determined by Gel Permeation Chromatography(GPC), as described in “Modern Size Exclusion Liquid Chromatographs”, W.W. Yan, J. J. Kirkland, and D. D. Bly, J. Wiley & Sons (1979); orestimated by ASTM D 2502; or estimated by freezing point depression, asdescribed in “Lange's Handbook of Chemistry”, 15th Edition, McGrawHill.The average carbon number (Cn) is calculated from Mn by Cn=(Mn−2)/14.

Processing Methods Blending

The components of the present invention can be blended by any suitablemeans. For example, they may be blended in a static mixer, batch mixer,extruder, or a combination thereof, that is sufficient to achieve anadequate dispersion of plasticizer in the polymer. The mixing step mayinvolve first dry blending using, for example, a tumble blender. It mayalso involve a “master batch” approach, where the final plasticizerconcentration is achieved by combining neat polymer with an appropriateamount of plasticized polymer that had been previously prepared at ahigher plasticizer concentration. Dispersion may take place as part of aprocessing method used to fabricate articles, such as in the extruder onan injection molding maching or fiber line. The plasticizer may beinjected into the extruder barrel or introduced at the feed throat ofthe extruder to save the step of preblending. This is a preferred methodwhen a larger percentage of plasticizer is to be used or largequantities of plasticized resin are desired.

Two general methods were used to generate examples of plasticizedblends. The first method is referred to as the Extruder Method, whereinthere are two approaches, “dry blending” and “direct injection”. The“dry blending” approach involves combining reactor granules of thepolymer with appropriate amounts of plasticizer and an additive package(including such components as antioxidants and nucleating agents) in atumble blender to achieve a homogeneous coarse mixing of components atthe desired plasticizer and additive concentrations. This was followedby compounding and pelletizing the blend using an extruder (either a 30or 57 mm twin screw extruder) at an appropriate extrusion temperatureabove the melting point of the polymer, but always in the range of200-230° C. In some cases, a sample of desired plasticizer concentrationwas produced in a similar manner by “dry blending” neat polymer pelletswith plasticized polymer pellets that had been blended previously at ahigher plasticizer concentration. The “direct injection” approachinvolved injecting warm plasticizer into the barrel of the extruder at apoint where the polymer has been melted. The plasticizer mass flow ratewas adjusted based on the polymer feed rate so as to achieve the desiredfinal plasticizer concentration. The blend was compounded in theremaining length of the extruder and subsequently pelletized.

The second method, which is referred to as the Brabender Method,involved mixing polymer pellets with the plasticizer in a heated C. W.Brabender Instruments Plasticorder to achieve a homogeneous melt at thedesired plasticizer concentration. The Brabender was equipped with aPrep-Mixer head (approximately 200 cm³ volume) and roller blades. Theoperating temperature was above the melting point of the polymer, butalways in the range of 180-190° C. Polymer was first melted in theBrabender for 1 minute at 60 RPM. Plasticizer was then added slowly toprevent pooling in the melted polymer. The blend was then mixed for 5minutes at 60 RPM under a nitrogen purge. The Brabender was opened andthe melt removed from the mixing head and blades as quickly as possible,and allowed to solidify. For those blends later subjected to injectionmolding, the pieces of material from the Brabender were cut into smallerpieces using a guillotine, then ground into even smaller pieces using aWiley Mill.

Injection Molding

For materials blended using the Extruder Method, standard ASTM tensileand flexure/HDT bars, and Gardner impact discs, were molded using 120ton injection molding equipment according to ASTM D4101. For materialsblended using the Brabender Method, tensile and flexure bars were moldedusing 20 ton injection molding equipment according to ASTM D4101, exceptfor the following provisions: the mold temperature was 40° C.; theinject time was 30 sec; the tensile and flex bars were of ASTM D638 TypeIV and ASTM D790 geometries, respectively; and the melt temperature was,in some cases, 10° C. off from the ASTM D4101-specified value, butalways in the range of 190-200° C. (except for the polybutene blends,which were molded with a melt temperature in the range of 220-230° C.).

Compression Molding

Material to be molded was placed between two sheets of PTFE-coatedaluminum foil onto a 0.125 inch thick chase, and pressed in a Carverpress at 160° C. The material was allowed to melt for 5 minutes withoutpressure applied, then compressed for 5 minutes at 10 tons pressure. Itwas then removed and immediately placed between water-cooled coldplatens and pressed for another 5 minutes at 10 tons pressure. Thefoil-sample-foil assembly was allowed to anneal for at least 40 hours atroom temperature, then quenched in dry ice prior to removing the samplefrom the foil to prevent deformation of the material when peeling offthe foil. Tensile and flexure specimens were died out of the sample onceit warmed to room temperature.

Spunbond Fabric Process

A typical spunbond process consists of a continuous filament extrusion,followed by drawing, web formation by the use of some type of ejector,and bonding the web. The polymer pellets are first fed into an extruder.In the extruder, the pellets simultaneously are melted and forcedthrough the system by a heating melting screw. At the end of the screw,a spinning pump meters the molten polymer through a filter to aspinneret where the molten polymer is extruded under pressure throughcapillaries, at a rate of 0.4 grams per hole per minute. The spinneretcontains a few hundred capillaries, measuring 0.4 mm in diameter. Thepolymer is melted at about 30-50° C. above its melting point to achievesufficiently low melt viscosity for extrusion. The fibers exiting thespinneret are quenched and drawn into fine fibers measuring about 16microns in diameter. The solidified fiber is laid randomly on a movingbelt to form a random netlike structure known in the art as web. The 25basis weight (grams per square meter) of web is obtained by controllingthe belt moving speed. After web formation, the web is bonded to achieveits final strength using a heated textile calender known in the art asthermobond calender. The calender consists of two heated steel rolls;one roll is plain and the other bears a pattern of raised points. Theweb is conveyed to the calender wherein a fabric is formed by pressingthe web between the rolls at a bonding temperature of ˜138° C.

Cast Film Process

Cast films were prepared using the following operations. Cast monolayerfilms were fabricated on a Killion cast film line. This line has three24:1 L/D 2.54 cm diameter extruder, which feed polymer into a feedblock.The feedblock diverts molten polymer from the extruder to a 20.32 cmwide Cloeren die. Molten polymer exits the die at a temperature of 230°C. and is cast on a chill roll (20.3 cm diameter, 25.4 cm roll face) at21° C. The casting unit is equipped with adjustable winding speeds toobtain film of the targeted thickness.

Sheet Extrusion

Sheet samples were extruded on a Reifenhauser Mirex-W sheet extruder.The extruder has an 80-mm, 33:1 L/D, barrier screw with Maddox andpineapple mixing sections. The sheet die has a symmetrical, coathangermanifold. The extruded sheets were quenched subsequently by a set ofchill rolls running in an upstack configuration. Each of the threepolished chill rolls has independent temperature control.

Methods for Determining NFP Content in Blend Method 1: Extraction

One method to determine the amount of NFP in a blend is Soxhletextraction, wherein at least a majority of the NFP is extracted withrefluxing n-heptane. Analysis of the base polymer is also requiredbecause it may contain low molecular weight and/or amorphous materialthat is soluble in refluxing n-heptane. The level of plasticizer in theblend is determined by correcting its extractables level, in weightpercent, by the extractables level for the base polymer, as describedbelow.

The Soxhlet extraction apparatus consists of a 400 ml Soxhlet extractor,with a widened overflow tube (to prevent siphoning and to provideconstant flow extraction); a metal screen cage fitted inside the mainSoxhlet chamber; a Soxhlet extraction thimble (Whatman, singlethickness, cellulose) placed inside the screen cage; a condenser withcooling water and drain; and a one-neck 1000 ml round bottom flask withappropriately sized stir bar and heating mantle.

The procedure is as follows. Dry the soxhlet thimbles in a 95° C. ovenfor ˜60 minutes. Weigh the dry thimble directly after removal from oven;record this weight as A: Thimble Weight Before, in g. Weigh out 15-20grams of sample (either in pellet or ground pellet form) into thethimble; record as B: Polymer Weight, in g. Place the thimble containingthe polymer in the Soxhlet apparatus. Pour about 300 ml of HPLC-graden-heptane into the round bottom flask with stir bar and secure the flaskon the heating mantle. Connect the round bottom flask, the soxhlet, andthe condenser in series. Pour more n-heptane down through the center ofthe condenser into the Soxhlet main chamber until the solvent level isjust below the top of the overflow tube. Turn on the cooling water tothe condenser. Turn on the heating mantle and adjust the setting togenerate a rolling boil in the round bottom flask and maintain a goodreflux. Allow to reflux for 16 hours. Turn the heat off but leave thecooling system on. Allow the system to cool down to room temperature.Disassemble the apparatus. Remove the thimble and rinse with a smallamount of fresh n-heptane. Allow to air dry in the laboratory hood,followed by oven drying at 95° C. for 90 minutes. Weigh the thimblecontaining the polymer directly after removal from oven; record as C:Polymer/Thimble Weight After, in g.

The quantity of extract is determined by calculating the weight lossfrom the sample, W=(A+B−C), in g. The extractables level, E, in weightpercent, is then calculated by E=100(W/B). The plasticizer content inthe blend, P, in weight percent, is calculated by P=E(blend)−E(basepolymer).

Method 2: Crystallization Analysis Fractionation (CRYSTAF)

Another method to determine the amount of NFP in a blend isfractionation using the Crystallization Analysis Fractionation (CRYSTAF)technique. This technique involves dissolving a sample in a solvent athigh temperature, then cooling the solution slowly to causefractionation of the sample based on solubility. For semi-crystallinesamples, including blends, solubility depends primarily oncrystallizability: portions of the sample that are more crystalline willprecipitate out of solution at a higher temperature than portions of thesample that are less crystalline. The relative amount of sample insolution as a function of temperature is measured using an infrared (IR)detector to obtain the cumulative solubility distribution. The solublefraction (SF) is defined as the IR signal at the lowest temperaturedivided by the IR signal when all the sample is dissolved at hightemperature, and corresponds to the weight fraction of sample that hasnot crystallized.

In the case of plasticized polyolefins, the plasticizer is mostlyamorphous and therefore contributes to the SF. Thus, the SF will belarger for blends with higher plasticizer content. This relationship isexploited to determine the plasticizer content of a blend of knowncomposition (polymer and plasticizer types) but unknown concentration. Acalibration curve that describes the SF as a function of plasticizercontent is developed by making a series of physical blends of knownconcentration using the same polymer and plasticizer materials, and thenanalyzing these blends under the same run conditions as used for blendsof unknown concentration. This series of calibrants must includeplasticizer concentrations above and below the concentration of theunknown sample(s), but not greater than 50 weight percent plasticizer,in order to reliably apply the calibration curve to the unknownsample(s). Typically, a linear fit of the calibration points is found toprovide a good description of the SF as a function of plasticizercontent (R²>0.9); other functional forms with 2 or fewer fittingparameters may be used if they improve the goodness-of-fit (increaseR²).

A commercial CRYSTAF 200 instrument (Polymer Char S. A., Valencia,Spain) with five stirred stainless steel vessels of 60 mL volume wasused to perform this test. Approximately 30 mg of sample were dissolvedfor 60 min at 160° C. in 30 mL of 1,2-dichlorobenzene that wasstabilized with 2 g/4 L of butylated hydroxytoluene. The solution wasthen stabilized for 45 min at 100° C. The crystallization was carriedout from 100 to 30° C. at a crystallization rate of 0.2° C./min. A dualwavelength infrared detector with a heated flow through cell maintainedat 150° C. was used to measure the polymer concentration in solution atregular intervals during the crystallization cycle; the measuringwavelength was 3.5 μm and the reference wavelength was 3.6 μm.

EXAMPLES

The present invention, while not meant to be limiting by, may be betterunderstood by reference to the following examples and tables. Thepolymers and fluids used in the examples are described in Tables 4 and5.

Examples in Tables 6-14 Based on Blends Made Using the Extruder Method

Samples 1-9 in Tables 6 and 9 were blended using the Extruder Method;the additive package contained 600 ppm of Irganox 1076 and 260 ppm ofcalcium stearate; a 57 mm twin-screw extruder was used at an extrusiontemperature of 230° C. Samples 10-14 in Tables 7 and 10 were blendedusing the Extruder Method; the additive package contained 825 ppmcalcium stearate, 800 ppm of Ultranox 626, 500 ppm of Tinuvin 622, and2500 ppm of Millad 3940; a 30 mm twin-screw extruder was used at anextrusion temperature of 216° C. Samples 15-19 in Tables 8 and 11 wereblended using the Extruder Method; the additive package contained 800ppm of calcium stearate, 1500 ppm of Irganox 1010, 500 ppm of Ultranox626, and 675 ppm of sodium benzoate; a 30 mm twin-screw extruder wasused at an extrusion temperature of 205° C. Samples 20-24 in Table 12were made by dry blending neat polymer pellets with previously blendedpellets of higher plasticizer concentration (Samples 6-9) to attain thedesired plasticizer concentration.

The resin properties of these samples are listed in Tables 6-8. Theaddition of NFP in the propylene polymers improve melt flowability, asindicated by the significant increase of melt flow rate. The improvementof melt flowability can be characterized by the decrease of shearviscosity as a function of shear rate range, as illustrated in FIGS.11-13. In contrast to a peroxide degrading (or so called “vis-breaking”)process, the increase of melt flowability in the current invention ismainly due to the plasticizing effect of the NFP; the polymer molecularweight is unchanged. This is evident in the comparison of molecularweight distribution, as shown in FIG. 14. The improvement of meltflowability usually benefits fabrication processes (for example, fiberspinning, film casting, extrusion, and injection molding) in terms ofbetter draw-down, lower extruder torque, thin wall injection, and fastercycle time.

The NFP in the current invention provides a significant depression inthe storage modulus of propylene polymers. As illustrated in FIG. 1, thestorage modulus of plasticized propylene polymers are drasticallyreduced as a function of temperature relative to the unplasticizedpolyolefins. A propylene polymer having lower a storage modulus (or“elastic modulus”) at any particular temperature indicates betterflexibility for the end-use at that particular temperature.

The NFP in the current invention demonstrates the ability to depressT_(g) without altering the melting temperature and crystallizationtemperature of propylene polymers, as illustrated in FIGS. 5-10.Traditional methods to depress T_(g) include the incorporation ofcomonomers as in the case for the propylene copolymers, which alsodepresses the melting temperature and crystallization temperature ofpolymer. Polymers having lower T_(g) without compromising the meltingcharacteristics are very desirable and can provide better impactresistance, particularly for below freezing temperature impactresistance, while maintaining the ability for high temperature usage.The plasticized polyolefins of the present invention provide this.

The NFP in the current invention is miscible with the propylene polymer,as determined by, for example, the single T_(g) profile of theplasticized propylene homopolymer and propylene copolymer. This is showngraphically in FIGS. 2-3. The NFP in the current invention is alsomiscible with the propylene impact copolymer, as determined by, forexample, the two T_(g) profile of the plasticized propylene impactcopolymer, one being the lower T_(g) profile for the ethylene-propylenerubber phase and one being the higher T_(g) profile for the propylenepolymer phase. This is shown graphically in FIG. 4.

Summaries of injection molded properties for these samples are providedin Tables 9-11. Molded parts from the invention plasticizedpolypropylene homopolymers show a significant decrease in flexural andtensile modulus at a loading of 4 wt % PAO or isoparaffin, whilemaintaining their tensile strength, room temperature Izod impactresistance and heat deflection temperature. For comparison, moldedsamples were also prepared with erucamide (cis-13-docosenoamide fromCrompton), a common lubricant designed to reduce molded part surfacefriction of 4 wt % concentration. The effect of the erucamide on theflexural modulus is insignificant, as shown in Table 12.

The addition of NFP substantially improves the impact resistance ofmolded parts without the significant decrease of heat deflectiontemperature. For example, Gardner impact strength, at both room andfreezing temperatures, has improved from 350% to 400% for propylenehomopolymers, from 140 to 165% for propylene copolymers, and from 20 to40% for propylene impact copolymers due to the addition of 4-5 wt % ofNFP. It is anticipated that further increase of impact resistance isattainable by the increase of NFP concentration in the propylenepolymers. Other measures of impact resistance, including Izod impact atroom and freezing temperatures, are also significantly improved.

Another advantage of the current invention is that the heat deflectiontemperature of plasticized polyolefins is not compromised (eithermaintained or only slightly reduced) which is crucial for applicationsrequiring maintenance of molded article dimensions at high temperature.Further indication of toughness improvement is shown by the significantincrease of elongation at yield and break. Many applications requiregood conformability during the end-use. A higher elongation facilitatesthe compliance of molded articles to the deformation during either theconversion process or at the end-use.

The NFP also demonstrate the ability to provide substantial softnessimprovement in spunbond nonwoven fabrics, as provided by the lower“total hand” in Table 13. In many applications, particularly in personalhygiene and health care, a soft nonwoven is very desirable for skincontact comfort. The current invention not only provides the improvementin softness but also maintains the necessary tensile strength, tearresistance and fabric uniformity.

Comparison of cast film properties are listed in Table 14. The NFP,particularly the Isopar-V plasticized propylene homopolymer (Sample 2)provides improvement in the tear and impact resistance, as indicated bythe relatively high (relative to the unplasticized polyolefin) Elmendorftear in both machine direction (MD) and transverse direction (TD) anddart impact at both room and freezing temperatures. In addition, theoptical properties, i.e., haze and gloss, are also improved. Theimprovement offers advantages in many film applications, for examples,food packaging, stationery cover, tape, medical and electronicpackaging.

Examples Fabricated from Blends Made Using the Brabender Method

Samples presented in Tables 15-24 were blended using the BrabenderMethod. The data in these tables show similar benefits as those inTables 6-13. Flowability is enhanced by the addition of the NFP as seenin the increase of MFR. Low temperature toughness increases as evidencedby the rise in Notched Izod at −18° C. Softness is enhanced as seen by adrop in flexural modulus. The Tg drops can be substantial, but themelting point and crystallization point remains essentially unchanged(to within 1-2° C.).

Examples in Tables 25-26 Based on Blends Made Using the Extruder Method

The data in tables 25 and 26 show similar benefits. Flowability isenhanced by the addition of the NFP as seen in the increase of MFR.Toughness increases as evidenced by the rise in impact properties.Softness is enhanced as seen by a drop in flexural modulus, but HDT islargely unaffected. The Tg drops can be substantial, but the meltingpoint and crystallization point remains essentially unchanged (to within1-2° C.).

Examples in Table 27 Showing Plasticizer Permanence

The loss of plasticizer as a function of time at elevated temperatureprovides a way to assess permanence of the plasticizer. The results inTable 27 for plasticized propylene random copolymer demonstrate theimportance of molecular weight of the plasticizer. The plasticizers werePAO liquids of increasing molecular weight and a white mineral oil. Eachplasticized sample was prepared by dry blending granules of thepropylene polymer with 10 wt % plasticizer, then was melt mixed using asingle-screw extruder to make pellets. A portion was compression moldedinto 0.25 mm thick sheets for emission testing conducted according toASTM D1203. Test specimens were 50 mm in diameter. The testingtemperature was 70° C. Specimens were weighed at 0, 24, 48, 139, 167,and 311 hours, and percentage of weight loss calculated. Over theprolonged time period examined, only the highest molecular weight PAOdid not show any additional weight loss than observed for the neatpolymer. Notably, the mineral oil exhibits significantly lowerpermanence than PAO liquids of comparable KV at 100° C. (>5 wt % lost at311 hr vs. 1-2 wt % lost for PAO).

Examples in Table 28 Showing Plasticizer Content

The measured plasticizer content in the final blend is compared to theoriginal plasticizer content before blending for severalresin/plasticizer combinations in Table 28. Extraction and CRYSTAFmethod results are compared. In general, there is good agreement betweenthe original blend composition based on component weights and the finalcomposition determined by the analytical methods.

Examples in Tables 29, 30, and 31

Blends of propylene random copolymers and fluids were prepared bymelt-mixing in a single-screw compounding extruder (Extruder Method withdirect injection of fluid into the barrel). Standard ASTM test specimenswere prepared using a 70-ton injection molder.

Molded parts from the fluid-enhanced RCPs show significant softening(particularly in terms of a decrease in flexural modulus and increase inelongation at break) and improved impact strength (particularly at lowtemperature). At the same time, other desirable properties are notsignificantly affected by addition of fluid, including good opticalproperties (haze and gloss) and heat deflection temperature. Flexibilityand low temperature impact strength increase with the increasing fluidlevel, allowing properties to be tailored to meet end-use requirements.

Examples in Tables 32 and 33

Blends of RCPs with 5 wt % of PAO or different levels of plastomer wereprepared by melt-mixing in a twin-screw compounding extruder (ExtruderMethod). Sheet samples were extruded on a Reifenhauser Mirex-W sheetextruder The extruder has an 80-mm, 33:1 L/D, barrier screw with Maddoxand pineapple mixing sections. The sheet die has a symmetrical,coathanger manifold. The extruded sheets were quenched subsequently by aset of chill rolls running in an upstack configuration. Each of thethree polished chill rolls has independent temperature control. Theextrusion conditions are listed in Table 32. Sheet properties aresummarized in Table 33.

The addition of only 5 wt % PAO produces a similar increase inflexibility as adding 20 wt % of plastomer (as evidenced by the FlexMod, which is the 1% secant flexure modulus) and produces a similarimprovement in impact strength as 40 wt % plastomer1 (as evidenced bythe Gardner impact, which is the Gardner impact strength at roomtemperature), while still maintaining excellent clarity and gloss.

Examples in Table 34

Blends of RCP with 5 wt % PAO, plastomer, or mVLDPE were prepared bymelt-mixing in a twin-screw compounding extruder (Extruder Method).Standard ASTM test specimens were prepared using a 70-ton injectionmolder.

Comparison of physical properties is presented in Table 34. Blends ofRCP with PAO shows significantly lower flexural modulus, higher impactstrength, and lower haze than blends with plastomer or mVLDPE. Theseresults indicate that fluids such as PAO are highly efficient inmodifying RCP relative to plastomer and mVLDPE.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to many differentvariations not illustrated herein. For these reasons, then, referenceshould be made solely to the appended claims for purposes of determiningthe scope of the present invention. Further, certain features of thepresent invention are described in terms of a set of numerical upperlimits and a set of numerical lower limits. It should be appreciatedthat ranges formed by any combination of these limits are within thescope of the invention unless otherwise indicated.

All priority documents are herein fully incorporated by reference forall jurisdictions in which such incorporation is permitted. Further, alldocuments cited herein, including testing procedures, are herein fullyincorporated by reference for all jurisdictions in which suchincorporation is permitted.

TABLE 4 List of Commercial Polymers used in Examples PolymerDescription* Source znPP Z-N isotactic propylene homopolymer, 12 MFR PP1024 E4, ExxonMobil Chemical mPP-1 metallocene isotactic propylenehomopolymer, 24 MFR, T_(m) ~152° C. Achieve ™ 3854, ExxonMobil ChemicalmPP-2 metallocene isotactic propylene homopolymer, 16 MFR Achieve ™1654, ExxonMobil Chemical sPP syndiotactic propylene homopolymer, 2.2MFR, 93% syndiotactic, Aldrich Chemicals, Catalog # 452149 T_(m) ~125°C., M_(w)~174 kg/mole, M_(n)~75 kg/mole RCP-1 Z-N propylene randomcopolymer, 12 MFR, T_(m) ~152° C. Clarified PP 9054, ExxonMobil ChemicalRCP-2 Z-N propylene random copolymer, 7 MFR, T_(m) ~146° C. PP 9513,ExxonMobil Chemical RCP-3 Z-N propylene random copolymer, 12 MFR PP 9374MED, ExxonMobil Chemical RCP-4 Z-N propylene random copolymer, 12 MFR PP9574 E6, ExxonMobil Chemical ICP-1 Z-N propylene impact copolymer, 21MFR, T_(m) ~163° C. PP 7684 E2, ExxonMobil Chemical ICP-2 Z-N propyleneimpact copolymer, 8 MFR PP 7033, ExxonMobil Chemical ICP-3 Z-N propyleneimpact copolymer, nucleated, 8 MFR PP 7033N, ExxonMobil Chemical TPOpropylene-based thermoplastic polyolefin containing 70 wt % 70 wt %Achieve ™ 3854, 30 wt % Exact ® metallocene isotactic propylenehomopolymer and 30 wt % 4033, ExxonMobil Chemical metalloceneethylene-butene copolymer (0.88 g/cm³ density, 0.8 MI) PB isotactic1-butene homopolymer, 0.4 MI, T_(m) ~125° C., M_(w)~570 kg/mole AldrichChemicals, Catalog # 189391 List of Experimental Polymers used inExamples Polymer Description EP-1 metallocene propylene-ethylenecopolymer, 9 MFR, 11 wt % ethylene made according to EP 1 003 814B1using dimethylaniliniumtetrakis-(pentafluorophenyl) borate anddimethylsilylbis(indenyl)hafnium dimethyl EP-2 metallocenepropylene-ethylene copolymer, 14 MFR, 14 wt % ethylene made according toEP 1 003 814B1 using dimethylaniliniumtetrakis(pentafluorophenyl) borateand dimethylsilylbis(indenyl)hafnium dimethyl RCP-5 experimentalpropylene-ethylene random copolymer, synthesized using a Ziegler-Nattacatalyst; MFR ~12 dg/min; M_(w)/M_(n) > 3.5; ethylene content ~2.2 wt %;additive package of 0.08% Ultranox-626, 0.0825% calcium stearate, 0.05%Tinuvin-622, and 0.25% Millad-3940 RCP-6 experimental propylene-ethylenerandom copolymer, synthesized using a Ziegler-Natta catalyst; MFR ~1.5dg/min; M_(w)/M_(n) > 3.5; ethylene content ~3 wt %; additive package of0.05% Ethanox-330, 0.05% Irgafos-168, and 0.08% calcium stearate RCP-7experimental propylene-ethylene random copolymer, synthesized using aZiegler-Natta catalyst; MFR ~4 dg/min; M_(w)/M_(n) > 3.5; ethylenecontent ~4.5 wt %; additive package of 0.125% Irganox-1010, 0.055% BHT,and 0.03% DHT-4A RCP-8 experimental propylene-ethylene random copolymer,synthesized using a Ziegler-Natta catalyst; MFR ~1.5 dg/min;M_(w)/M_(n) > 3.5; ethylene content ~3 wt %; additive package of 0.05%Irganox-1010, 0.05% Irgafos-168, 0.04% calcium stearate, 0.08% glycerolmono-stearate, and 0.15% Millad-3988 RCP-9 experimentalpropylene-ethylene random copolymer, synthesized using a Ziegler-Nattacatalyst; MFR ~4 dg/min; M_(w)/M_(n) > 3.5; ethylene content ~4.5 wt %;additive package of 0.05% Irganox-1010, 0.05% Irgafos-168, 0.04% calciumstearate, 0.08% glycerol mono-stearate, and 0.15% Millad-3988 RCP-10experimental propylene-ethylene random copolymer, synthesized using aZiegler-Natta catalyst; MFR ~9 dg/min; M_(w)/M_(n) > 3.5; ethylenecontent ~1.9 wt %; additive package of 0.05% Irganox-1076, 0.1%Irgafos-168, 0.065% calcium stearate, 0.025% glycerol mono-stearate, and0.15% Millad-3988 *“Z-N” indicates a Ziegler-Natta type catalyst usedfor synthesis “metallocene” indicates a metallocene type catalyst usedfor synthesis

TABLE 5 List of Fluids used as Plasticizers in Examples FluidDescription Source SHF-21 PAO liquid ExxonMobil Chemical SHF-41 PAOliquid ExxonMobil Chemical SHF-61 PAO liquid ExxonMobil Chemical SHF-82PAO liquid ExxonMobil Chemical SHF-101 PAO liquid (also SpectraSyn ™ExxonMobil Chemical 10) SHF-403 PAO liquid (also SpectraSyn ™ ExxonMobilChemical 40) SHF-1003 PAO liquid (also SpectraSyn ™ 100) SuperSyn 2150PAO liquid (also SpectraSyn ExxonMobil Chemical Ultra ™ 150) SuperSynPAO liquid ExxonMobil Chemical 23000 Rudol white mineral oil CromptonFreezene 200 white mineral oil Crompton ParaLux 6001R paraffinic processoil Chevron Isopar V isoparaffinic hydrocarbon fluid ExxonMobil ChemicalNorpar 15 normal paraffinic hydrocarbon ExxonMobil Chemical fluid ExxsolD130 dearomatized aliphatic ExxonMobil Chemical hydrocarbon fluid CORE2500 Group I basestock ExxonMobil Chemical EHC 110 Group II basestockExxonMobil Chemical VISOM 6 Group III basestock ExxonMobil ChemicalVHVI-8 Group III basestock PetroCanada GTL6/MBS Group III basestockExxonMobil Chemical GTL14/HBS Group III basestock ExxonMobil ChemicalTPC 137 polyisobutylene liquid Texas Petrochemicals Lucant HC-10 Blendof decene oligomer with Mitsui Chemicals an ethylene/α-olefin liquidAmerica C-9900 polybutene liquid Infineum Properties of PAO Fluids usedas Plasticizers in Examples KV, KV, pour Mn 40° C. 100° C. VI point (g/specific Fluid (cSt) (cSt) (—) (° C.) mole) Cn gravity SHF-21 5 <2 N.D.−66   280^(#) 20 0.798 SHF-41 19 4 126 −66   450^(#) 32 0.820 SHF-61 316 138 −57   540^(#) 38 0.827 SHF-82 48 8 139 −48   640^(#) 46 0.833SHF-101 66 10 137 −48   720^(#) 51 0.835 SHF-403 396 39 147 −36  1,700⁺120 0.850 SHF-1003 1240 100 170 −30  3,000⁺ 210 0.853 SuperSyn 1,500 150218 −33  3,700⁺ 260 0.850 2150 SuperSyn 35,000 2,800 360 −9 18,800⁺1,340 0.855 23000 Rudol 29 5 103 −24   400 28 0.86^(a) Freezene 39 5 38−42   350 25 0.88^(a) 200 ParaLux 116 12 99 −12   580 41 0.87 6001RIsopar V 9 <2 N.D. −63   240^(#) 17 0.82 Norpar 15 2 <2 N.D. 7   210^(#)15 0.77 Exxsol 4 <2 N.D. −6   250^(#) 18 0.83 D130 CORE 490 32 95 −6  800* 57 0.896 2500 EHC 110 99 11 95 −12   500* 36 0.860 VISOM 6 35 7148 −18   510* 36 0.836 VHVI-8 50 8 129 −12   560 40 0.850 GTL6/ 30 6156 −18   510* 36 0.823 MBS GTL14/ 95 14 155 −24   750* 53 0.834 HBS TPC137 30 6 132 −51   350 25 0.845 Lucant 60 10 150 −53   590 42 0.826^(b)HC-10 C-9900 140 12 60 −36   540 38 0.846 List of Polymer Modifiers usedin Examples Modifier Description Source plastomer1 ethylene octenecopolymer produced using Exact ™ an Exxpol ® metallocene catalyst; melt0201 index ~1.1 dg/min (ASTM D1238, 190° C., ExxonMobil 2.16 kg load);density ~0.902 g/cm³ Chemical plastomer2 ethylene octene copolymerproduced using Exact ™ an Exxpol ® metallocene catalyst; 0203 melt index~3.0 dg/min (ASTM D1238, ExxonMobil 190° C., 2.16 kg load); density~0.902 g/cm³ Chemical mVLDPE Ethylene hexene copolymer produced usingExceed ™ an Exxpol ® metallocene catalyst; 1012CA melt index ~1.0 dg/min(ASTM D1238, ExxonMobil 190° C., 2.16 kg load); density ~0.912 g/cm³Chemical N.D. = not defined, due to KV at 100° C. <2 cSt. Mn reported bymanufacturer or estimated according to ASTM D2502, except as indicated:*estimated by freezing point depression, ^(#)measured by GC, ⁺measuredby GPC. Specific gravity at 60° F. (15.6° C.) except ^(a) at 25° C. or^(b) at 20° C.

TABLE 6 Resin properties of plasticized mPP-1 propylene homopolymerSample No. 1 2 3 4 5 6 7 8 9 NFP none Isopar-V SHF-101 SHF-403 SuperSyn-Isopar-V SHF-403 SuperSyn- SuperSyn- 2150 2150 23000 Concentration ofNFP (wt %) 0 4 4 4 4 10 10 10 10 Resin Properties MFR 23 32 29 29 29 5145 39 37 Melting Temperature (° C.) 152 151 153 152 153 152 151 152 152Crystallization Temperature (° C.) 115 115 118 118 118 115 116 115 115Glass Transition Temperature 4 −1 −1 0 2 −11 −5 −3 1 (° C.)

TABLE 7 Resin properties of plasticized RCP-1 propylene random copolymerSample No. 10 11 12 13 14 NFP None Isopar-V SHF-101 SHF-403SuperSyn-2150 Concentration of NFP (wt %) 0 5 5 5 5 Resin Properties MFR12 16 16 15 15 Melting Temperature (° C.) 152 152 152 152 152Crystallization Temperature (° C.) 122 121 121 121 121 Glass TransitionTemperature (° C.) 1 −7 −5 −3 −1

TABLE 8 Resin properties of plasticized ICP-1 propylene impact copolymerSample No. 15 16 17 18 19 NFP none Isopar-V SHF-101 SHF-403SuperSyn-2150 Concentration of NFP (wt %) 0 5 5 5 5 Resin PropertiesMelt Flow Rate 23 32 29 29 29 Melting Temperature (° C.) 163 162 162 162162 Crystallization Temperature (° C.) 119 120 120 120 121 GlassTransition Temperature (° C.) −53, 5.2 −55, −3 −56, −4 −50, −1 −52, 1

TABLE 9 Molded part properties of plasticized mPP-1 propylenehomopolymer Sample No. 1 2 3 4 5 NFP: none Isopar V SHF-101 SHF-403SuperSyn-2150 Concentration of NFP (wt %) 0 4  4  4  4 OpticalProperties Haze (%) 65 62  65  61  64 Gloss @ 45° 85 87  86  85  86Mechanical Properties Tensile Strength @ Yield (kpsi) 4.9 4.4    4.5   4.5    4.6 Elongation @ Yield (%) 9 12  11  11  10 Flexural Modulus,1% Secant (kpsi) 200 155 175 177 179 Heat Deflection Temperature @ 66psi 105 101 108 107 104 (° C.) Rockwell Hardness (R-Scale) 104 97  99 99  99 Impact Properties Notched Izod Impact @ 23° C. (ft-lb/in) 0.40.7    0.6    0.6    0.5 Gardner Impact Strength @ 23° C. (in-lb) 31 153166 164 141 Gardner Impact Strength @ 0° C. (in-lb) —^(a) 14   <8^(b)  <8^(b)   <8^(b) ^(a)Samples too brittle to perform this test.^(b)Samples failed at the lowest hammer weight.

TABLE 10 Molded part properties of plasticized RCP-1 propylene randomcopolymer Sample No. 10 11 12 13 14 NFP: None Isopar V SHF-101 SHF-403SuperSyn-2150 Concentration of NFP (wt %) 0 5 5 5 5 Optical PropertiesHaze (%) 8.2 10.3 8.7 11.7 11.6 Gloss @ 45° 80 81 79 75 76 MechanicalProperties Tensile Strength @ Yield (kpsi) 5.0 4.4 4.4 4.4 4.4Elongation @ Yield (%) 9 14 13 11 11 Elongation @ Break (%) 185 754 559259 196 Flexural Modulus, 1% Secant (kpsi) 205 141 158 166 173 HeatDeflection Temperature @ 66 psi (° C.) 87 84 85 77 77 Impact PropertiesNotched Izod Impact @ 23° C. (ft-lb/in) 0.9 2.0 1.2 1.2 1.2 ReversedNotched Izod Impact @ −18° C. (ft-lb/in) 3.9 12.6 12.4 10.5 9.0 GardnerImpact Strength @ 23° C. (in-lb) 83 203 207 201 219

TABLE 11 Molded part properties of plasticized ICP-1 propylene impactcopolymer Sample No. 15 16 17 18 19 NFP: None Isopar V SHF-101 SHF-403SuperSyn-2150 Concentration of NFP (wt %) 0 5 5 5 5 MechanicalProperties Tensile Strength @ Yield (kpsi) 3.3 3.0 3.0 3.0 3.0Elongation @ Yield (%) 5 12 10 8 8 Elongation @ Break (%) 125 230 185120 110 Flexural Modulus, 1% Secant (kpsi) 163 112 124 132 135 HeatDeflection Temperature @ 66 psi (° C.) 95 81 88 84 86 Impact PropertiesNotched Izod Impact @ 23° C. (ft-lb/in) 4.8 6.5 6.0 3.9 3.5 GardnerImpact Strength @ −29° C. (in-lb) 123 170 165 159 148

TABLE 12 Molded part properties of plasticized mPP-1 propylenehomopolymer Sample No. 20 21 22 23 24 NFP None Isopar V SHF-403SuperSyn-23000 Erucamide Concentration of NFP (%) 0 4 4 4 4 ResinProperties MFR 24 35 33 30 23 Mechanical Properties Tensile Strength @Yield (kpsi) 4.7 4.5 4.4 4.5 4.5 Elongation @ Yield (%) 9 11 11 10 11Flexural Modulus, 1% Secant (kpsi) 190 155 170 180 188 Heat DeflectionTemperature @ 66 psi (° C.) 92 94 90 90 89 Impact Properties NotchedIzod Impact @ 23° C. (ft-lb/in) 0.4 0.5 0.3 0.4 0.4 Reverse Notched IzodImpact @ −18° C. (ft-lb/in) 2.7 3.1 3.0 n/a n/a

TABLE 13 Softness properties of spunbond nonwoven fabrics made ofplasticized mPP-1 propylene homopolymer Sample No. 1 2 3 4 5 NFP: noneIsopar V SHF-101 SHF-403 SuperSyn-2150 Concentration of NFP (%)  0  4  4 4  4 Fabric Properties Peak Load (lbs) MD/TD 9.4/4.8 8.0/4.4 7.8/4.18.3/4.1 7.5/3.9 Elongation @ Break (%) MD/TD 76/77 65/76 58/67 72/7364/73 Elmendorf Tear (g/basis weight) TD 17 19 15 18 20 Total Hand(grams) 31 32 24 21 15 Properties per total hand. Total hand is based onmeasurements on fabrics at 25 gsm (grams per square meter).

TABLE 14 Cast film properties of plasticized mPP-1 propylene homopolymerSample No. 1 2 3 4 5 NFP: none Isopar V SHF-101 SHF-403 SuperSyn-2150Concentration of NFP (%) 0 4 4 4 4 Optical Properties Haze (%) 8.8 6.216.7 14.7 10.5 Gloss 68 70 57 58 65 Mechanical Properties 1% Sec.Modulus (kpsi) MD/TD 140/130 84/86 119/120 133/121 120/115 TensileStrength @ Break (kpsi) MD/TD 7.6/7.8 7.5/7.1 7.1/7.5 7.2/7.0 7.0/6.9Elongation @ Break (%) MD/TD 730/728 725/680 770/792 785/765 738/739Elmendorf Tear (g/mil) MD 29/32 54/58 17/19 17/18 22/24 Puncture(lb/mil) 9.0 8.1 8.6 8.6 9.2 Puncture Energy (in.lb/mil) 18 21 19 17 20Total Energy Dart Impact (ft.lb) @ 23° C. 0.4 1.9 0.6 0.7 0.6 @ −15° C.0.04 0.07 0.09 0.09 0.05 Film properties are based on 2 mil thickness.

TABLE 15 Tensile modulus and yield properties for plasticized znPPpropylene homopolymer Plasticizer Young's Yield Yield Energy to contentModulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi) (%)(ft-lbf) — 0 130.2 4934 12.4 21.0 Rudol 5 92.1 4578 17.8 27.3 Rudol 1075.2 3947 21.6 28.5 SHF-101 5 98.5 4614 17.3 26.9 SHF-101 10 78.9 384423.3 31.2 SHF-101 20 48.7 2658 44.1 41.8 SHF-403 5 102.2 4547 16.9 26.5SHF-403 10 86.4 4006 20.0 27.3 SuperSyn 2150 5 108.8 4736 16.1 26.4SuperSyn 2150 10 88.5 4131 19.3 26.9 Isopar V 5 93.4 4716 17.8 28.0IsoPar V 10 70.3 4100 20.9 28.0 Norpar 15 5 90.3 4627 17.7 27.2 Norpar15 10 80.4 4304 20.5 28.7 Exxsol D130 5 87.8 4628 18.3 28.1 Exxsol D13010 71.5 4038 21.9 29.0 CORE 2500 5 103.3 4720 17.0 27.2 EHC 110 5 98.94680 17.6 27.9 VISOM 6 5 92.4 4576 17.8 27.3 VHVI-8 5 92.4 4577 17.827.4 GTL6/MBS 5 92.3 4526 18.6 28.2 GTL14/HBS 5 97.1 4525 18.3 28.2 TPC137 5 94.5 4617 18.3 28.6 Lucant HC-10 5 97.9 4701 17.8 28.3 C-9900 5100.3 4641 17.6 27.8 Tensile break properties for plasticized znPPpropylene homopolymer Plasticizer Break Break Energy to content stressStrain Break Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 3428 63972.5 Rudol 5 3080 643 71.2 Rudol 10 3093 663 69.9 SHF-101 5 3121 70077.5 SHF-101 10 3003 683 71.6 SHF-101 20 2632 53 4.3 SHF-403 5 3003 60867.3 SHF-403 10 2953 620 65.2 SuperSyn 2150 5 3027 521 58.5 SuperSyn2150 10 2875 413 43.7 Isopar V 5 3212 672 75.2 IsoPar V 10 3380 717 76.9Norpar 15 5 3516 714 79.9 Norpar 15 10 3451 678 73.8 Exxsol D130 5 3339708 78.6 Exxsol D130 10 3482 693 74.1 CORE 2500 5 3092 741 81.8 EHC 1105 3142 690 76.7 VISOM 6 5 3146 687 76.4 VHVI-8 5 3190 696 78.4 GTL6/MBS5 3484 699 78.4 GTL14/HBS 5 3235 687 76.6 TPC 137 5 3195 725 79.7 LucantHC-10 5 3128 699 78.3 C-9900 5 3276 698 77.1 Flexure and Notched Izodimpact properties for plasticized znPP propylene homopolymer −18° C.RNI* Plasticizer 1% Secant 2% Secant impact Plasticizer content ModulusModulus resistance type (wt %) (kpsi) (kpsi) (ft-lb/in) — 0 189.6 171.52.7 Rudol 5 145.4 128.7 4.3 Rudol 10 107.9 94.7 10.1 SHF-101 5 153.8135.7 4.7 SHF-101 10 116.0 101.2 13.0 SHF-101 20 65.8 57.7 6.3 SHF-403 5163.8 145.2 3.0 SHF-403 10 123.4 107.9 8.7 SuperSyn 5 170.2 151.5 3.12150 SuperSyn 10 132.2 115.8 7.2 2150 Isopar V 5 145.6 128.9 3.6 IsoParV 10 109.2 96.3 10.2 Norpar 15 5 143.6 126.8 8.2 Norpar 15 10 120.8106.0 12.1 Exxsol D130 5 138.7 122.1 7.8 Exxsol D130 10 106.8 94.3 14.7CORE 2500 5 155.4 137.8 2.8 EHC 110 5 146.6 129.6 3.3 VISOM 6 5 147.6130.1 7.7 VHVI-8 5 147.3 130.0 5.9 GTL6/MBS 5 144.4 126.8 8.5 GTL14/ 5160.8 140.2 7.4 HBS TPC 137 5 145.5 128.8 6.2 Lucant HC- 5 148.5 130.56.2 10 C-9900 5 146.7 129.9 3.2 *Results were obtained using theReversed Notched Izod testing protocol (ASTM D256E). Rheologicalproperties for plasticized znPP propylene homopolymer PlasticizerPlasticizer content η₀ λ MFR type (wt %) (Pa · s) (s) N (g/10 min) — 02243 0.075 0.325 11.51 Rudol 5 Rudol 10 1334 0.057 0.328 32.22 SHF-101 51786 0.067 0.324 SHF-101 10 1311 0.053 0.311 31.75 SHF-101 20 753 0.0390.309 SHF-403 5 1827 0.068 0.323 18.99 SHF-403 10 1366 0.055 0.314 29.01SuperSyn 5 1822 0.069 0.323 17.93 2150 SuperSyn 10 1385 0.056 0.323 2150Isopar V 5 1876 0.068 0.329 IsoPar V 10 1414 0.059 0.332 28.74 Norpar 155 1943 0.071 0.334 Norpar 15 10 1698 0.069 0.335 28.85 Exxsol D130 51927 0.071 0.331 16.78 Exxsol D130 10 1583 0.063 0.327 CORE 2500 5 EHC110 5 1835 0.069 0.327 17.52 VISOM 6 5 1780 0.068 0.326 18.16 VHVI-8 51764 0.064 0.323 20.27 GTL6/MBS 5 1745 0.065 0.322 GTL14/ 5 1828 0.0690.322 HBS TPC 137 5 1834 0.068 0.327 23.19 Lucant HC- 5 1776 0.066 0.31817.10 10 C-9900 5 1816 0.068 0.325 DSC properties for plasticized znPPpropylene homopolymer T_(m) T_(m) at onset, at peak, ΔH_(f), Plasticizerfirst first first T_(c) at T_(c) at content heating heating heatingonset peak Plasticizer type (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) — 0166.0 95.8 114.7 109.0 Rudol 5 150.8 166.9 98.6 117.1 108.0 Rudol 10150.0 163.7 87.7 116.3 109.5 SHF-101 5 151.7 167.1 93.8 118.4 110.0SHF-101 10 151.2 164.7 86.6 116.6 108.7 SHF-101 20 149.3 162.4 79.5113.1 106.8 SHF-403 5 151.0 167.4 89.2 117.6 109.2 SHF-403 10 152.9165.6 86.8 117.5 110.6 SuperSyn 2150 5 151.5 167.7 102.3 118.9 110.6SuperSyn 2150 10 153.6 166.1 88.0 117.0 110.9 Isopar V 5 148.9 166.692.3 116.7 110.0 IsoPar V 10 149.4 163.9 82.8 116.5 107.6 Norpar 15 5149.1 166.2 98.2 116.5 109.3 Norpar 15 10 151.6 165.3 86.7 117.5 109.6Exxsol D130 5 150.4 166.6 89.5 117.1 109.6 Exxsol D130 10 CORE 2500 5152.4 167.6 91.5 116.0 106.5 EHC 110 5 150.8 167.0 91.0 116.3 108.4VISOM 6 5 151.6 167.0 94.4 117.4 108.7 VHVI-8 5 150.1 167.3 87.7 116.7109.4 GTL6/MBS 5 GTL14/HBS 5 TPC 137 5 151.8 167.6 85.2 117.0 108.8Lucant HC-10 5 C-9900 5 149.9 166.8 94.4 117.2 109.9 DSC properties forplasticized znPP propylene homopolymer T_(m) T_(m) at onset, at peak,ΔH_(f), Plasticizer second second second Plasticizer content heatingheating heating type (wt %) (° C.) (° C.) (J/g) — 0 161.4 96.2 Rudol 5153.4 164.5 102.0 Rudol 10 151.1 158.5 93.3 SHF-101 5 154.0 164.9 94.2SHF-101 10 151.6 159.4 85.4 SHF-101 20 146.9 161.0 81.4 SHF-403 5 154.6166.0 93.5 SHF-403 10 153.5 160.7 94.8 SuperSyn 5 154.7 165.8 107.8 2150SuperSyn 10 154.4 161.0 98.4 2150 Isopar V 5 154.0 164.9 101.8 IsoPar V10 153.8 164.9 95.0 Norpar 15 5 154.4 164.7 97.5 Norpar 15 10 155.1161.0 97.0 Exxsol 5 154.4 165.2 91.6 D130 Exxsol 10 D130 CORE 5 153.2166.5 97.5 2500 EHC 110 5 153.0 165.3 98.9 VISOM 6 5 153.2 165.1 101.3VHVI-8 5 153.8 164.6 96.2 GTL6/ 5 MBS GTL14/ 5 HBS TPC 137 5 154.2 165.791.2 Lucant 5 HC-10 C-9900 5 153.2 165.2 102.6 DMTA properties forplasticized znPP propylene homopolymer Plasticizer T_(g) T_(g) contentat onset at peak Peak Plasticizer type (wt %) (° C.) (° C.) Area — 0−9.7 4.7 0.19 Rudol 5 −39.4 −5.2 0.61 Rudol 10 −51.5 −10.4 0.70 SHF-1015 −44.0 −5.9 0.51 SHF-101 10 −54.9 −12.1 0.65 SHF-101 20 −78.7 −36.90.94 SHF-403 5 −39.0 −3.8 0.45 SHF-403 10 −45.2 −7.0 0.62 SuperSyn 21505 −36.9 −0.5 0.26 SuperSyn 2150 10 −41.5 −6.9 0.49 Isopar V 5 −33.5 −4.60.41 IsoPar V 10 −46.9 −10.7 0.73 Norpar 15 5 −46.1 −9.0 0.38 Norpar 1510 −46.6 −16.4 0.57 Exxsol D130 5 −40.2 −9.4 0.60 Exxsol D130 10 CORE2500 5 −34.3 −0.7 0.36 EHC 110 5 −36.3 −3.1 0.47 VISOM 6 5 −47.3 −6.40.47 VHVI-8 5 −39.7 −8.2 −0.56 GTL6/MBS 5 GTL14/HBS 5 TPC 137 5 −38.7−5.25 0.45 Lucant HC-10 5 −39 −5.2 0.39 C-9900 5 −33.5 −5 0.46 DMTAproperties for plasticized znPP propylene homopolymer Plasticizer E′ E′content before T_(g) at 25° C. Plasticizer type (wt %) (MPa) (MPa) — 03199 1356 Rudol 5 3250 714 Rudol 10 4040 919 SHF-101 5 3201 915 SHF-10110 3776 986 SHF-101 20 3209 522 SHF-403 5 3056 739 SHF-403 10 3001 726SuperSyn 2150 5 3047 929 SuperSyn 2150 10 2829 685 Isopar V 5 2681 853IsoPar V 10 3437 673 Norpar 15 5 4037 1210 Norpar 15 10 3623 1034 ExxsolD130 5 2973 723 Exxsol D130 10 CORE 2500 5 3716 1170 EHC 110 5 3193 743VISOM 6 5 3782 1009 VHVI-8 5 3459 847 GTL6/MBS 5 GTL14/HBS 5 TPC 137 52836 784 Lucant HC-10 5 3165 762 C-9900 5 2808 835.6

TABLE 16 Tensile modulus and yield properties for plasticized mPP-1propylene homopolymer Plasticizer Young's Yield Yield Energy toPlasticizer content Modulus Stress Strain Yield type (wt %) (kpsi) (psi)(%) (ft-lbf) — 0 132.3 4983 11.3 18.9 Rudol 10 68.9 3852 20.5 26.5Freezene 200 10 65.6 3930 20.5 26.9 SHF-403 5 88.1 4338 15.5 22.9SHF-403 10 70.9 3888 18.8 25.1 CORE 2500 10 70.0 3869 18.7 24.6 VISOM 610 59.1 3574 21.3 25.9 C-9900 10 65.6 3778 20.3 26.0 Tensile breakproperties for plasticized mPP-1 propylene homopolymer Plasticizer BreakBreak Energy to content stress Strain Break Plasticizer type (wt %)(psi) (%) (ft-lbf) — 0 3336 654 69.1 Rudol 10 4307 853 92.1 Freezene 20010 4414 875 95.4 SHF-403 5 4375 857 92.6 SHF-403 10 4235 866 92.7 CORE2500 10 4234 858 91.2 VISOM 6 10 4150 851 88.1 C-9900 10 4249 906 95.3Flexure and Notched Izod impact properties for plasticized mPP-1propylene homopolymer Plasticizer 1% Secant 2% Secant −18° C. RNI*Plasticizer content Modulus Modulus impact resistance type (wt %) (kpsi)(kpsi) (ft-lb/in) — 0 180.4 165.8 2.5 Rudol 10 99.6 89.5 10.2 Freezene200 10 102.6 91.8 5.7 SHF-403 5 156.9 141.3 2.6 SHF-403 10 120.5 106.95.8 CORE 2500 10 114.3 101.5 4.4 VISOM 6 10 106.3 94.4 13.3 C-9900 10104.9 93.8 5.8 Rheological properties for plasticized mPP-1 propylenehomopolymer Plasticizer Plasticizer content η₀ λ MFR type (wt %) (Pa ·s) (s) n (g/10 min) — 0 830 0.012 0.190 25.54 Rudol 10 515 0.009 0.15550.21 Freezene 200 10 519 0.009 0.185 47.04 SHF-403 5 SHF-403 10 5210.009 0.135 CORE 2500 10 527 0.009 0.137 VISOM 6 10 C-9900 10 515 0.0090.173 DSC properties for plasticized mPP-1 propylene homopolymer T_(m)T_(m) ΔH_(f), T_(m) T_(m) ΔH_(f), Plasticizer at onset, first at peak,first first T_(c) at T_(c) at at onset, at peak, second secondPlasticizer content heating heating heating onset peak second heatingheating heating type (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) (° C.) (°C.) (J/g) — 0 151.4 79.1 109.1 104.2 149.5 89.2 Rudol 10 133.0 149.670.2 107.1 102.6 138.7 105.9 77.5 Freezene 200 10 133.3 149.4 73.7 107.4104.0 138.6 147.5 85.2 SHF-403 5 SHF-403 10 135.9 151.3 74.7 108.6 103.5139.9 149.2 82.6 CORE 2500 10 134.8 151.4 74.5 107.1 101.2 139.3 147.478.3 VISOM 6 10 C-9900 10 DMTA properties for plasticized mPP-1propylene homopolymer Plasticizer T_(g) T_(g) E′ E′ content at onset atpeak Peak before T_(g) at 25° C. Plasticizer type (wt %) (° C.) (° C.)Area (MPa) (MPa) — 0 −15.4 5.6 0.19 2179 807 Rudol 10 −46.2 −7.9 0.623894 898 Freezene 200 10 −36.3 −5.2 0.64 3497 571 SHF-403 5 SHF-403 10−42.0 −6.8 0.47 2884 702 CORE 2500 10 −68.0 −51.7 0.07 3472 601 VISOM 610 C-9900 10 −41.1 −8.8 0.71 3139 673 *Results were obtained using theReversed Notched Izod testing protocol (ASTM D256E).

TABLE 17 Tensile modulus and yield properties for plasticized RCP-2propylene random copolymer Plasticizer Young's Yield Yield Energy tocontent Modulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi)(%) (ft-lbf) —  0 75.2 3997 17.0 23.0 Rudol 10 39.8 3126 26.5 27.6ParaLux 6001R 10 45.8 3156 26.0 27.8 SuperSyn 2150 10 49.6 3192 24.727.0 EHC 110 10 41.1 3129 26.5 27.9 VISOM 6 10 38.5 3114 26.7 27.8GTL14/HBS 10 43.6 3160 26.5 28.2 Tensile break properties forplasticized RCP-2 propylene random copolymer Plasticizer Break BreakEnergy to content stress Strain Break Plasticizer type (wt %) (psi) (%)(ft-lbf) —  0 4422 710 82.0 Rudol 10 4883 1057 127.1 ParaLux 6001R 103919 763 79.4 SuperSyn 2150 10 4568 1006 116.7 EHC 110 10 4793 1039123.8 VISOM 6 10 4751 1096 128.8 GTL14/HBS 10 4865 1052 127.4 Flexureand Notched Izod impact properties for plasticized RCP-2 propylenerandom copolymer Plasticizer 1% Secant 2% Secant −18° C. RNI* contentModulus Modulus impact resistance Plasticizer type (wt %) (kpsi) (kpsi)(ft-lb/in) —  0 121.2  109.7  3.0 Rudol 10 67.8 60.2 26.2 ParaLux 6001R10 75.2 66.8 20.9 SuperSyn 2150 10 82.6 72.4 16.2 EHC 110 10 70.4 62.621.6 VISOM 6 10 71.8 63.6 30.0** GTL14/HBS 10 76.6 67.3 27.2 Rheologicalproperties for plasticized RCP-2 propylene random copolymer Plasticizercontent η₀ λ MFR Plasticizer type (wt %) (Pa · s) (s) n (g/10 min) —  04467 0.120 0.297  7.20 Rudol 10 2605 0.124 0.352 ParaLux 6001R 10 19.30SuperSyn 2150 10 2752 0.125 0.345 15.38 EHC 110 10 VISOM 6 10 2514 0.1140.345 16.59 GTL14/HBS 10 DSC properties for plasticized RCP-2 propylenerandom copolymer T_(m) T_(m) ΔH_(f), T_(m) T_(m) ΔH_(f), Plasticizer atonset, first at peak, first first T_(c) at T_(c) at at onset, at peak,second second Plasticizer content heating heating heating onset peaksecond heating heating heating type (wt %) (° C.) (° C.) (J/g) (° C.) (°C.) (° C.) (° C.) (J/g) —  0 149.7 67.9 104.1 99.2 146.2 77.9 Rudol 10122.0 147.0 65.2 101.7 95.2 130.1 141.2 61.5 ParaLux 10 6001R SuperSyn10 127.1 149.3 70.8 104.9 97.4 133.2 143.4 69.7 2150 EHC 110 10 123.7148.2 67.2 101.4 94.8 130.6 144.3 64.3 VISOM 6 10 125.1 148.6 65.1 101.394.5 130.3 144.8 65.6 GTL14/HBS 10 DMTA properties for plasticized RCP-2propylene random copolymer Plasticizer T_(g) T_(g) E′ E′ content atonset at peak Peak before T_(g) at 25° C. Plasticizer type (wt %) (° C.)(° C.) Area (MPa) (MPa) —  0 −19.8 −1.9 0.39 3344 1038  Rudol 10 −48.8−10.0 1.03 3992 600 ParaLux 6001R 10 −48.0 −11.5 0.87 3263 472 SuperSyn2150 10 −39.7 −6.7 0.70 3086 510 EHC 110 10 −46.4 −9.8 0.91 3503 464VISOM 6 10 −59.5 −15.7 0.83 3425 481 GTL14/HBS 10 *Results were obtainedusing the Reversed Notched Izod testing protocol (ASTM D256E). **SomeRNI failures were incomplete breaks.

TABLE 18 Tensile modulus and yield properties for plasticized EP-1propylene-ethylene copolymer Plasticizer Young's Yield Yield contentModulus Stress* Strain* Plasticizer type (wt %) (kpsi) (psi) (%) —  04.23 564 24 Rudol 10 2.68 434 27 SHF-101 10 2.78 442 27 VHVI-8 10 2.74449 28 TPC 137 10 2.78 456 28 Lucant HC-10 10 2.50 453 30 C-9900 10 2.82444 27 *Compression-molded test specimens; yield determined using 10%off-set definition. Tensile break properties for plasticized EP-1propylene- ethylene copolymer Plasticizer Break Break Energy to contentstress Strain Break Plasticizer type (wt %) (psi) (%) (ft-lbf) —  0 28961791 94.5 Rudol 10 * * * SHF-101 10 * * * VHVI-8 10 2679 1930 88.8 TPC137 10 * * * Lucant HC-10 10 2947 1883 87.7 C-9900 10 2865 1861 85.2 *Majority of specimens did not break before maximum strain limit reached.Flexure properties for plasticized EP-1 propylene-ethylene copolymerPlasticizer 1% Secant 2% Secant content Modulus Modulus Plasticizer type(wt %) (kpsi) (kpsi) —  0 5.854 5.816 Rudol 10 4.598 4.456 SHF-101 104.668 4.448 VHVI-8 10 4.895 4.786 TPC 137 10 4.579 4.439 Lucant HC-10 104.615 4.506 C-9900 10 4.568 4.437 Rheological properties plasticizedEP-1 propylene-ethylene copolymer Plasticizer content η₀ λ MFRPlasticizer type (wt %) (Pa · s) (s) n (g/10 min) —  0 2032 0.022 0.252Rudol 10 SHF-101 10 VHVI-8 10 TPC 137 10 Lucant HC-10 10 C-9900 10 DSCproperties for plasticized EP-1 propylene-ethylene copolymer T_(m) T_(m)ΔH_(f), T_(m) T_(m) ΔH_(f), Plasticizer at onset, at peak, first firstT_(c) at T_(c) at at onset, second at peak, second second Plasticizercontent first heating heating heating onset peak heating heating heatingtype (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) (° C.) (° C.) (J/g) —  041.8 55.6 34.3 22.6  8.3 33.7 61.4 20.9 Rudol 10 40.5 51.8 25.5 29.822.0 41.2 50.8, 67.2 19.2 SHF-101 10 38.3 51.4 29.0 32.2 25.1 48.6 57.8,67.0 18.3 VHVI-8 10 TPC 137 10 Lucant HC- 10 10 C-9900 10 DMTAproperties for plasticized EP-1 propylene-ethylene copolymer PlasticizerT_(g) T_(g) E′ E′ Content at onset at peak Peak before T_(g) at 25° C.Plasticizer type (wt %) (° C.) (° C.) Area (MPa) (MPa) —  0 −24.5* Rudol10 −35.5 −21.8 3.7 2515 16.1 SHF-101 10 −38.2 −22.5 4.3 3196 18.7 VHVI-810 −38.3 −22.1 4.4 3307 36.1 TPC 137 10 −38.0 −23.1 3.2 3028 26.9 LucantHC-10 10 C-9900 10 *As measured by DSC.

TABLE 19 Tensile modulus and yield properties for plasticized EP-2propylene-ethylene copolymer Plasticizer Young's Yield Yield contentModulus Stress* Strain* Plasticizer type (wt %) (kpsi) (psi) (%) —  01.457 246 28 Rudol 10 0.846 128 28 Freezene 200 10 1.043 181 29 SHF-40310 0.886 143 27 IsoPar V 10 0.793 124 27 Exxsol D130 10 0.833 125 28GTL6/MBS 10 1.092 189 28 *Compression-molded test specimens; yielddetermined using 10% off-set definition. Tensile break properties forplasticized EP-2 propylene- ethylene copolymer Plasticizer Break BreakEnergy to content stress Strain Break Plasticizer type (wt %) (psi) (%)(ft-lbf) —  0 * * * Rudol 10 * * * Freezene 200 10 * * * SHF-40310 * * * IsoPar V 10 * * * Exxsol D130 10 * * * GTL6/MBS 10 * * * *Majority of specimens did not break before maximum strain limit reached.Flexure properties for plasticized EP-2 propylene-ethylene copolymerPlasticizer 1% Secant 2% Secant content Modulus Modulus Plasticizer type(wt %) (kpsi) (kpsi) —  0 2.354 2.267 Rudol 10 1.856 1.791 Freezene 20010 2.032 1.920 SHF-403 10 1.930 1.884 IsoPar V 10 1.521 1.502 ExxsolD130 10 1.775 1.733 GTL6/MBS 10 1.942 1.858 Rheological properties forplasticized EP-2 propylene-ethylene copolymer Plasticizer content η₀ λMFR Plasticizer type (wt %) (Pa · s) (s) n (g/10 min) —  0 1167 0.0110.194 Rudol 10 Freezene 200 10 SHF-403 10 IsoPar V 10 Exxsol D130 10GTL6/MBS 10 DSC properties for plasticized EP-2 propylene-ethylenecopolymer T_(m) T_(m) ΔH_(f), T_(m) T_(m) ΔH_(f), Plasticizer at onset,first at peak, first first T_(c) at T_(c) at at onset, at peak, secondsecond Plasticizer content heating heating heating onset peak secondheating heating heating type (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) (°C.) (° C.) (J/g) —  0 39.7 47.0 13.4 — — — — — Rudol 10 40.2 50.8 10.1 —— 44.7 56.2 3.5 Freezene 200 10 SHF-403 10 39.0 49.7 14.2 — — 44.4 54.34.9 IsoPar V 10 Exxsol D130 10 42.1 49.5 10.2 — — — — — GTL6/MBS 10 DMTAproperties for plasticized EP-2 propylene-ethylene copolymer PlasticizerT_(g) T_(g) E′ E′ content at onset at peak Peak before T_(g) at 25° C.Plasticizer type (wt %) (° C.) (° C.) Area (MPa) (MPa) —  0 −30.8* Rudol10 Freezene 200 10 SHF-403 10 IsoPar V 10 Exxsol D130 10 GTL6/MBS 10 *Asmeasured by DSC.

TABLE 20 Tensile modulus and yield properties for plasticized sPPpropylene homopolymer Plasticizer Young's Yield Yield Energy to contentModulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi) (%)(ft-lbf) —  0 36.7 2481 21.7 17.7 Rudol 10 21.9 1991 31.5 20.7 IsoPar V10 23.3 2057 28.9 19.5 VHVI-8 10 22.9 2047 32.9 22.6 Tensile breakproperties for plasticized sPP propylene homopolymer Plasticizer BreakBreak Energy to content stress Strain Break Plasticizer type (wt %)(psi) (%) (ft-lbf) —  0 2321 254 19.8 Rudol 10 2288 338 23.3 IsoPar V 102260 341 23.7 VHVI-8 10 2347 355 25.1 Flexure and Notched Izod impactproperties for plasticized sPP propylene homopolymer −18° C. RNI*Plasticizer 1% Secant 2% Secant impact content Modulus Modulusresistance Plasticizer type (wt %) (kpsi) (kpsi) (ft-lb/in) —  0 64.260.8 3.4 Rudol 10 39.5 37.3 5.0 IsoPar V 10 41.8 39.4 4.8 VHVI-8 10 41.739.1 31.9** Rheological properties for plasticized sPP propylenehomopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa ·s) (s) n (g/10 min) —  0 12431 0.179 0.307 Rudol 10 6823 0.136 0.328IsoPar V 10 7445 0.143 0.325 VHVI-8 10 6652 0.131 0.327 DSC propertiesfor plasticized sPP propylene homopolymer T_(m) T_(m) ΔH_(f), T_(m)T_(m) ΔH_(f), Plasticizer at onset, first at peak, first first T_(c) atT_(c) at at onset, second at peak, second second Plasticizer contentheating heating heating onset peak heating heating heating type (wt %)(° C.) (° C.) (J/g) (° C.) (° C.) (° C.) (° C.) (J/g) —  0 116.9 128.939.0 81.9 70.7 — — — Rudol 10 IsoPar V 10 VHVI-8 10 114.0 127.0 34.280.8 72.2 116.1 127.5 33.9 DMTA properties for plasticized sPP propylenehomopolymer E′ Plasticizer T_(g) T_(g) before E′ content at onset atpeak Peak T_(g) at 25° C. Plasticizer type (wt %) (° C.) (° C.) Area(MPa) (MPa) —  0 −4.8 8.4 1 2717 434 Rudol 10 −31.6 −6.7 1.8 3637 360IsoPar V 10 −26.9 −4.8 1.5 3462 373 VHVI-8 10 −35.5 −4.8 1.53 3141 221*Results were obtained using the Reversed Notched Izod testing protocol(ASTM D256E). **All RNI specimens did not break.

TABLE 21 Tensile modulus and yield properties for plasticized ICP-2propylene impact copolymer Plasticizer Young's Yield Yield Energy tocontent Modulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi)(%) (ft-lbf) — 0 99.2 3766 10.7 13.3 Rudol 10 54.9 2985 23.0 23.9ParaLux 6001R 10 57.5 3022 21.8 22.9 SHF-101 10 61.3 3076 22.2 23.9Exxsol D130 10 43.9 2950 25.2 25.7 EHC 110 10 60.1 3096 22.4 24.1 TPC137 10 54.0 2959 23.0 23.8 Tensile break properties for plasticizedICP-2 propylene impact copolymer Plasticizer Break Break Energy tocontent stress Strain Break Plasticizer type (wt %) (psi) (%) (ft-lbf) —0 2221 394 38.8 Rudol 10 3430 763 76.0 ParaLux 6001R 10 3236 777 77.6SHF-101 10 3572 774 78.9 Exxsol D130 10 4020 1063 117.2 EHC 110 10 3474681 68.2 TPC 137 10 3124 776 76.3 Flexure and Notched Izod impactproperties for plasticized ICP-2 propylene impact copolymer Plasticizer1% Secant 2% Secant −18° C. NI content Modulus Modulus impact resistancePlasticizer type (wt %) (kpsi) (kpsi) (ft-lb/in) — 0 144.1 129.7 1.1Rudol 10 83.8 73.8 1.3 ParaLux 6001R 10 86.8 76.7 1.3 SHF-101 10 96.182.6 1.3 Exxsol D130 10 82.9 72.4 1.7 EHC 110 10 92.6 80.1 1.3 TPC 13710 88.8 77.9 1.5 Rheological properties for plasticized ICP-2 propyleneimpact copolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %)(Pa · s) (s) n (g/10 min) — 0 4218 0.182 0.368 8.164 Rudol 10 2663 0.1420.370 22.26 ParaLux 6001R 10 30.95 SHF-101 10 Exxsol D130 10 2765 0.1520.375 EHC 110 10 2745 0.144 0.367 18.89 TPC 137 10 2438 0.110 0.35927.11 DSC properties for plasticized ICP-2 propylene impact copolymerT_(m) T_(m) ΔH_(f), T_(m) T_(m) ΔH_(f), Plasticizer at onset, first atpeak, first first T_(c) at T_(c) at at onset, second at peak, secondsecond Plasticizer content heating heating heating onset peak heatingheating heating type (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) (° C.) (°C.) (J/g) — 0 166.6 76.9 114.8 111.3 163.2 85.6 Rudol 10 149.4 163.472.8 114.7 108.1 151.3 158.7 76.7 ParaLux 10 149.2 165.1 73.1 113.2106.1 150.4 163.6 74.6 6001R SHF-101 10 Exxsol D130 10 EHC 110 10 149.0165.2 72.4 115.8 107 151.5 163.9 76.5 TPC 137 10 149.5 166.0 72.0 116.2106.5 152.3 164.2 76.4 DMTA properties for plasticized ICP-2 propyleneimpact copolymer Plasticizer Lower T_(g) Lower T_(g) Lower Upper T_(g)Upper T_(g) Upper E′ E′ Plasticizer content at onset at peak Peak atonset at peak Peak before T_(g) at 25° C. type (wt %) (° C.) (° C.) Area(° C.) (° C.) Area (MPa) (MPa) — 0 −56.4 −50.2 0.06 −24.5 2.9 0.20 2269557 Rudol 10 −63.5 −53.0 0.08 −41.5 −7.7 0.50 2854 514 ParaLux 10 −57.9−50.8 0.07 −39.2 −7.2 0.43 3425 689 6001R SHF-101 10 Exxsol D130 10−71.6 −59.8 0.19 −34.2 −10.5 0.25 3515 558 EHC 110 10 −60.0 −50.6 0.07−37.0 −9.0 0.43 3116 589 TPC 137 10 −71.4 −59.7 0.11 −43.4 −13.0 0.403065 579

TABLE 22 Tensile modulus and yield properties for plasticized ICP-3propylene impact copolymer Plasticizer Young's Yield Yield Energy tocontent Modulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi)(%) (ft-lbf) — 0 123.5 4151 8.5 11.1 ParaLux 6001R 10 68.2 3199 22.325.5 SuperSyn 2150 10 76.4 3319 17.0 19.6 Norpar 15 10 62.2 3236 24.527.7 GTL6/MBS 10 61.6 3207 26.1 29.7 Lucant HC-10 10 65.4 3153 24.8 27.8Tensile break properties for plasticized ICP-3 propylene impactcopolymer Plasticizer Break Break Energy to content stress Strain BreakPlasticizer type (wt %) (psi) (%) (ft-lbf) — 0 2894 88 10.3 ParaLux6001R 10 2578 614 60.3 SuperSyn 2150 10 2903 588 59.2 Norpar 15 10 3049584 58.1 GTL6/MBS 10 3079 558 56.0 Lucant HC-10 10 3043 567 55.8 Flexureand Notched Izod impact properties for plasticized ICP-3 propyleneimpact copolymer Plasticizer 1% Secant 2% Secant −18° C. NI contentModulus Modulus impact resistance Plasticizer type (wt %) (kpsi) (kpsi)(ft-lb/in) — 0 193.3 168.7 1.1 ParaLux 6001R 10 100.5 87.7 1.5 SuperSyn2150 10 120.3 102.2 1.3 Norpar 15 10 101.5 87.9 2.3 GTL6/MBS 10 103.287.9 1.8 Lucant HC-10 10 102.5 87.7 1.6 Rheological properties forplasticized ICP-3 propylene impact copolymer Plasticizer content η0 λMFR Plasticizer type (wt %) (Pa · s) (s) n (g/10 min) — 0 4301 0.1900.367 9.22 ParaLux 6001R 10 2455 0.129 0.354 18.77 SuperSyn 2150 10Norpar 15 10 3151 0.161 0.378 GTL6/MBS 10 Lucant HC-10 10 2452 0.1280.361 DSC properties for plasticized ICP-3 propylene impact copolymerT_(m) T_(m) ΔH_(f), T_(m) T_(m) ΔH_(f), Plasticizer at onset, first atpeak, first first T_(c) at T_(c) at at onset, second at peak, secondsecond Plasticizer content heating heating heating onset peak heatingheating heating type (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) (° C.) (°C.) (J/g) — 0 166.5 80.2 131.0 127.3 167.3 77.0 ParaLux 10 150.5 165.075.8 118.3 114.4 154.1 164.1 76.6 6001R SuperSyn 10 153.2 166.0 76.9122.1 84.4 156.1 165.5 80.7 2150 Norpar 15 10 GTL6/MBS 10 Lucant HC- 1010 DMTA properties for plasticized ICP-3 propylene impact copolymerPlasticizer Lower T_(g) Lower T_(g) Lower Upper T_(g) at Upper T_(g) atUpper E′ E′ Plasticizer content at onset at peak Peak onset peak Peakbefore T_(g) at 25° C. type (wt %) (° C.) (° C.) Area (° C.) (° C.) Area(MPa) (MPa) — 0 −57.9 −50.0 −13.2 4.1 3369 768.4 ParaLux 10 −59.3 −52.40.09 −35.2 −4.6 0.42 3037 661.4 6001R SuperSyn 10 −58.5 −49.9 0.06 −35.3−3.0 0.14 3297 716.3 2150 Norpar 15 10 −59.2 −52.2 0.03 −38.8 −11.2 0.363545 591.0 GTL6/MBS 10 Lucant HC- 10 −66.4 −58.3 0.10 −42.8 −9.1 0.403168 661.0 10

TABLE 23 Tensile modulus and yield properties for plasticized TPOpropylene-based thermoplastic olefin Plasticizer Young's Yield YieldEnergy to content Modulus Stress Strain Yield Plasticizer type (wt %)(kpsi) (psi) (%) (ft-lbf) — 0 68.7 3187 14.0 15.1 Rudol 10 38.1 224026.5 21.1 SHF-101 10 38.8 2189 25.2 19.9 IsoPar V 10 37.6 2304 26.5 21.4GTL14/HBS 10 39.6 2232 28.4 23.1 Tensile break properties forplasticized TPO propylene-based thermoplastic olefin Plasticizer BreakBreak Energy to content stress Strain Break Plasticizer type (wt %)(psi) (%) (ft-lbf) — 0 5154 1051 116.0 Rudol 10 5165 1334 151.9 SHF-10110 4780 1218 129.2 IsoPar V 10 5021 1276 141.2 GTL14/HBS 10 5148 1342154.6 Flexure and Notched Izod impact properties for plasticized TPOpropylene-based thermoplastic olefin Plasticizer 1% Secant 2% Secant−18° C. NI content Modulus Modulus impact resistance Plasticizer type(wt %) (kpsi) (kpsi) (ft-lb/in) — 0 116.0 105.8 1.0 Rudol 10 62.9 56.20.9 SHF-101 10 66.2 58.7 1.0 IsoPar V 10 61.5 55.1 1.1 GTL14/HBS 10 68.560.2 1.0 Rheological properties for plasticized TPO propylene-basedthermoplastic olefin Plasticizer content η₀ λ MFR Plasticizer type (wt%) (Pa · s) (s) n (g/10 min) — 0 1675 0.014 0.207 Rudol 10 SHF-101 10IsoPar V 10 GTL14/HBS 10 DSC properties for plasticized TPOpropylene-based thermoplastic olefin T_(m) T_(m) ΔH_(f), T_(m) T_(m)ΔH_(f), Plasticizer at onset, first at peak, first first T_(c) at T_(c)at at onset, second at peak, second second Plasticizer content heatingheating heating onset peak heating heating heating type (wt %) (° C.) (°C.) (J/g) (° C.) (° C.) (° C.) (° C.) (J/g) — 0 138.2 151.8 58.4 109.8103.7 142.5 150.1 64.0 Rudol 10 SHF-101 10 IsoPar V 10 GTL14/HBS 10 DMTAproperties for plasticized TPO propylene-based thermoplastic olefinPlasticizer Lower T_(g) at Lower T_(g) at Lower Upper T_(g) at UpperT_(g) at Upper E′ E′ Plasticizer content onset peak Peak onset peak Peakbefore T_(g) at 25° C. type (wt %) (° C.) (° C.) Area (° C.) (° C.) Area(MPa) (MPa) — 0 −60.6 −45.1 0.06 −8.7 6.0 0.15 2867 782 Rudol 10 −68.1−55.6 0.10 −34.2 −3.9 0.51 3169 425 SHF-101 10 −65.0 51.7 0.07 −34.3−7.0 0.30 3472 601 IsoPar V 10 −77.2 −57.8 0.14 −34.7 −6.9 0.42 3657 609GTL14/HBS 10

TABLE 24 Tensile modulus and yield properties for plasticized PB1-butene homopolymer Plasticizer Young's Yield Yield content ModulusStress Strain Plasticizer type (wt %) (kpsi) (psi) (%) — 0 55.0 * *Rudol 10 25.8 * * Norpar 15 10 26.3 * * VISOM 6 10 23.7 * * C-9900 1026.8 * * * No yield before failure. Tensile break properties forplasticized PB 1-butene homopolymer Plasticizer Break Break Energy tocontent stress Strain Break Plasticizer type (wt %) (psi) (%) (ft-lbf) —0 5200 38 5.0 Rudol 10 3289 31 2.4 Norpar 15 10 3349 31 2.5 VISOM 6 103238 31 2.3 C-9900 10 3139 25 1.8 Flexure and Notched Izod impactproperties for plasticized PB 1-butene homopolymer Plasticizer 1% Secant2% Secant −18° C. RNI* content Modulus Modulus impact resistancePlasticizer type (wt %) (kpsi) (kpsi) (ft-lb/in) — 0 79.7 74.0 17.7Rudol 10 37.0 35.2 18.1** Norpar 15 10 43.0 40.7 22.2** VISOM 6 10 36.635.2 19.2** C-9900 10 36.5 35.2 20.7** *Results were obtained using theReversed Notched Izod testing protocol (ASTM D256E). **Some NI failureswere incomplete breaks.

TABLE 25 Resin properties of plasticized mPP-2 propylene homopolymer TmTm Tc Tc Tg wt % peak onset ΔHm peak onset ΔHc peak PAO (° C.) (° C.)(J/g) (° C.) (° C.) (J/g) (° C.) Control 0 152.8 142.2 109.6 123.8 127.2106.0 3.5 SHF61 3 151.8 142.5 105.9 123.6 127.1 104.3 SHF61 5 151.5142.3 102.8 122.6 126.1 100.9 SHF61 10 149.7 140.9 100.4 120.8 124.495.6 SHF101 3 151.9 142.8 104.1 123.5 127.0 103.1 −0.4 SHF101 5 151.5142.6 102.2 123.0 126.6 100.4 −2.3 SHF101 10 150.3 140.9 99.5 120.8124.3 100.3 −6.4 SHF401 3 152.2 142.7 104.3 123.5 126.9 106.3 SHF401 5151.7 142.1 102.6 122.8 126.4 100.8 SHF401 10 151.0 142.2 97.8 121.8125.5 98.8 SuperSyn 2150 3 152.2 142.2 103.1 123.3 126.7 105.2 SuperSyn2150 5 151.9 143.0 101.3 123 126.5 99.2 SuperSyn 2150 10 151.4 142.196.0 121.8 125.3 98.7 Molded part properties of plasticized mPP-2propylene homopolymer Tensile Elongation Flex Gardner NI RNI wt %strength to yield 1% secant HDT RT RT −18° C. PAO MFR (kpsi) (%) (kpsi)(° C.) (in-lbs) (ft-lb/in) (ft-lb/in) Control 0 16.6 5.20 8.6 230 107.822 1.02 2.45 SHF61 3 19.7 4.86 12.4 187 107.5 194 1.27 2.63 SHF61 5 22.54.40 15.0 161 99.8 189 0.80 6.04 SHF61 10 28.1 3.89 16.6 133 98.9 2060.92 11.30 SHF101 3 19.5 4.73 12.8 188 104.1 167 0.68 2.75 SHF101 5 20.94.46 13.9 174 105.7 209 0.72 3.19 SHF101 10 26.7 3.85 16.5 140 95.7 2510.91 8.99 SHF401 3 19.3 4.68 11.7 199 104.7 157 0.57 2.27 SHF401 5 21.44.39 12.7 182 100.6 186 0.62 2.84 SHF401 10 26.8 3.96 14.9 153 96.9 1920.83 5.62 SuperSyn 2150 3 19.2 4.78 10.5 205 101.4 153 0.49 2.63SuperSyn 2150 5 21.6 4.53 12.1 190 104.3 182 0.64 2.78 SuperSyn 2150 1023.4 3.99 13.4 157 92.8 214 0.70 6.48

TABLE 26 Molded part properties of plasticized propylene randomcopolymers RCP-3 RCP-4 no NFP 25 wt % no NFP 5 wt % 5 wt % Properties(control) Exact ® 3035 (control) Isopar V SHF-101 Tensile strength @yield (psi) 4.7 3.2 4.2 4.0 4.0 Elongation @ yield (%) 12 16.7 13.4 16.717.2 Flex modulus 1% secant (kpsi) 167 102 146 108 116 HDT @ 66 psi (°C.) 84 70 78 73 72 Gardner impact @ 23° C. (in-lbs) 273 210 242 226 226Notched Izod impact @ 23° C. (ft-lbs/in) 1.1 10.3 1.4 4.5 3.8 Haze (%) —— 9.9 8.6 10.2 RCP-3 contains 800 ppm CaSt, 800 ppm Ultanox 626A, 500ppm Tinuvin 622, 2500 ppm Millad 3940 RCP-4 contains 400 ppm CaSt, 400ppm Irganox 3114, 400 ppm Ultanox 626A, 1500 ppm Millad 3940, 800 ppmAtmer 129 Exact ® 3035 is a metallocene ethylene-butene copolymer (3.5MI, 0.90 g/cm3 density)

TABLE 27 Comparison of permanence of NFP in RCP-2 propylene randomcopolymer. plasticizer % weight loss over time period KV at 139 Blendcomposition 100° C. 24 hr 48 hr hr 167 hr 311 hr PP — 0.3 0.3 0.3 0.30.3 PP + 10% SHF-21 2 7.7 8.1 8.1 8.0 8.0 PP + 10% SHF-41 4 0.2 0.7 1.11.3 2.0 PP + 10% SHF-61 6 0.2 0.4 0.6 0.6 0.9 PP + 10% SHF-82 8 0.1 0.20.3 0.3 0.5 PP + 10% SHF-101 10  −0.1 0.2 0.2 0.1 0.3 PP + 10% Rudol 5 —— — — 5.4

TABLE 28 NFP content in polypropylene/NFP blends. Dry blend extractionCRYSTAF Blend composition method method Polymer NFP Method (wt % NFP)(wt % NFP) (wt % NFP) Achieve ™ 1654 SHF-101 Extruder 3 2.6 2.2 ±0.1^(a) 5 4.5 4.2 ± 0.1^(a) 10 7.4 7.6 ± 0.1^(a) 20 15.4 15.2 ± 0.5^(a )PP 3155 SuperSyn 2150 Extruder 3 2.5^(b) 3.5 6 5.5^(b) 6.5 PP 1024SHF-101 Brabender 5 — 5.9 10 — 10.3  20 — 21.1  PP 1024 Isopar VBrabender 5 — 3.9 10 — 8.3 PP 7033N SuperSyn 2150 Brabender 10 9.9 —Norpar 15 Brabender 10 6.5 — GTL6/MBS Brabender 10 9.4 10.1  ^(a)Averageand standard deviation reported for results from triplicate CRYSTAFruns. ^(b)12 hour reflux.

TABLE 29 Molded part properties of RCP-5 with 5 wt % of differentfluids. None Isopar SHF-101 SHF-403 SuperSyn 2150 Concentration of fluid(wt %) 0 5 5 5 5 Optical Properties Haze (%) 8.2 10.3 8.7 11.7 11.6Gloss @ 45° 80 81 79 75 76 Mechanical Properties Tensile Strength @Yield (kpsi) 5.0 4.4 4.4 4.4 4.4 Elongation @ Yield (%) 9 14 13 11 11Elongation @ Break (%) 185 754 559 259 196 Flexural Modulus, 1% Secant(kpsi) 205 141 158 166 173 Heat Deflection Temperature @ 66 psi (° C.)87 84 85 77 77 Impact Properties Notched Izod Impact @ 23° C. (ft-lb/in)0.9 2.0 1.2 1.2 1.2 Unnotched Izod Impact @ −18° C. (ft-lb/in) 3.9 12.612.4 10.5 9.0 Gardner Impact Strength @ 23° C. (in-lb) 83 203 207 201219

TABLE 30 Molded part properties of RCP-6 with different level of PAOsNeat resin SHF-101 SHF-1003 Concentration (wt %) 0 5 10 15 5 10 15 MFR(dg/min) 1.5 7.6 8.6 6.9 5.7 4.8 3.9 Tensile Strength @ Yield (kpsi) 4.13.3 3.0 2.7 3.4 2.4 2.9 Elongation @ Yield (%) 13 17 20 23 16 15 23Flexural Modulus, 137 99 81 71 106 95 84 1% Secant (kpsi) GardnerImpact, 23° C. (in-lbs) 230 220 218 191 233 248 224 Notched Izod, 23° C.(ft-lbs/in) 0.7 0.7 0.9 0.8 0.8 1.3 1.5 Unnotched Izod, −18° C.(ft-lbs/in) 6 10.7 18.4 24.4 11.3 20.4 28.3

TABLE 31 Molded part properties of RCP-7 with different level of PAOsNeat SHF-101 SHF-1003 Concentration (wt %) 0 5 10 5 10 MFR (dg/min) 4.011.6 13.6 9.1 8.2 Tensile Strength @ Yield (kpsi) 3.2 2.7 2.4 2.8 2.5Elongation @ Yield (%) 15 19 21 18 21 Flexural Modulus, 88 78 63 78 681% Secant (kpsi) Gardner Impact, 23° C. (in-lbs) 239 229 225 238 245Notched Izod, 23° C. (ft-lbs/in) 1.4 1.1 1.1 1.3 1.6 Unnotched Izod,−18° C. (ft-lbs/in) 10.5 18.7 30.3 18.1 25.3

TABLE 32 Sheet extrusion conditions Base Blend MFR Extruder BarrelExtruder Die Melt Temp Chiller Roll Temp polymer (in wt %) (dg/min) Temp(° C.) Temp (° C.) (° C.) Top/Middle/Bottom (° C.) RCP-8 Neat 2 220 230236 55/65/55  5% SHF-101 2.1 220 230 250 55/65/55 10% Plastomer1 1.4 220230 252 55/65/55 20% Plastomer1 1.3 220 230 253 55/65/55 30% Plastomer11.5 220 230 253 55/65/55 40% Plastomer1 1.6 220 230 251 55/65/55 RCP-9Neat 6 210 220 232 55/65/55  5% SHF-101 11 210 220 222 55/65/55 10%Plastomer1 4 210 220 233 55/65/55 20% Plastomer1 4 210 220 233 55/65/55

TABLE 33 Comparison of sheet properties of RCP-8 and RCP-9 with SHF-101and Plastomer1 Base Blend Top Sheet Bottom Flex Mod Gardner impactpolymer (in wt %) Clarity Haze Gloss Sheet Gloss (kpsi) (in-lb) RCP-8Neat 93.8 43.8 90.0 95.0 154 74  5% SHF-101 94.4 41.1 88.8 92.7 111 11410% Plastomer1 95.0 39.5 88.8 95.0 125 102 20% Plastomer 1 90.0 34.586.0 85.0 112 104 30% Plastomer1 88.8 37.6 75.0 70.8 96 96 40%Plastomer1 76.9 38.0 64.4 45.0 74 115 RCP-9 Neat 87.5 35.3 89.4 90.0 11793  5% SHF-101 98.8 36.2 92.5 92.0 90 120 10% Plastomer1 97.5 34.5 88.892.5 103 108 20% Plastomer 1 98.1 36.3 93.1 91.5 91 100

TABLE 34 Molded part properties of RCP-10 with 5% SHF-101, Plastomer2and mVLDPE Neat SHF-101 Plastomer2 mVLDPE MFR (dg/min) 9 15 10 9 Haze(%) 11 9 10 14 Tensile Strength @ Yield 5.1 4.2 4.5 4.7 (kpsi)Elongation @ Yield (%) 10 15 12 12 Flexural Modulus, 1% 213 145 182 186Secant (kpsi) Heat Deflection 92 74 79 80 Temperature @ 66 psi (° C.)Notched Izod Impact 1.1 2.6 1.3 1.4 @ 23° C. (ft-lb/in) Unnotched IzodImpact 5.7 14.2 6.3 7.3 @ −18° C. (ft-lb/in) Gardner Impact Strength 183227 217 219 @ 23° C. (in-lb)

1.-129. (canceled)
 130. An article comprising a plasticized polyolefincomposition comprising one or more polypropylene impact copolymers orpolypropylene impact copolymer blends and one of more non-functionalizedplasticizers where the non-functionalized plasticizer comprises C₂₀ toC₁₅₀₀ paraffins having a kinematic viscosity of 10 cSt or more at 100°C. and a viscosity index of 120 or more.
 131. The article of claim 130wherein the propylene impact copolymer or blend comprises 40% to 95% byweight of a Component A and from 5% to 60% by weight of a Component Bbased on the total weight of copolymer; wherein Component A comprisespropylene homopolymer or copolymer, the copolymer comprising 10% or lessby weight ethylene, butene, hexene or octene comonomer; and whereinComponent B comprises propylene copolymer, wherein the copolymercomprises from 5% to 70% by weight ethylene, butene, hexene and/oroctene comonomer, and from 95% to 30% by weight propylene.
 132. Thearticle of claim 131 wherein the refractive index of Component A and therefractive index of Component B are within 10% of each other and,optionally, the refractive index of the non-functionalized plasticizeris within 20 % of Component A, Component B or both.
 133. The article ofclaim 130 wherein one or more polypropylene impact copolymers orpolypropylene impact copolymer blends is an in situ propylene impactcopolymer comprising from 40% to 95% by weight of a Component A and from5% to 60% by weight of a Component B based on the total weight ofcopolymer; wherein Component A comprises propylene homopolymer orcopolymer, the copolymer comprising 10% or less by weight ethylene,butene, hexene or octene comonomer; and wherein Component B comprisespropylene copolymer, wherein the copolymer comprises from 5% to 70% byweight ethylene, butene, hexene and/or octene comonomer, and from 95% to30% by weight propylene.
 134. The article of claim 130 wherein therefractive index of Component A and the refractive index of Component Bare within 10% of each other and, optionally, the refractive index ofthe non-functionalized plasticizer is within 20% of Component A,Component B or both.
 135. The article of claim 130, wherein thepolyolefin composition excludes physical blends of polypropylene withother polyolefins.
 136. The article of claim 135 wherein the polyolefincomposition excludes physical blends of one or more polypropylenes withpolyethylene or polyethylene copolymers having a molecular weight of 500to 10,000 g/mol.
 137. The article of claim 130 where the one or morepolypropylene impact copolymers or polypropylene impact copolymer blendscomprises a random copolymer of propylene and up to 5 weight % ofethylene.
 138. The article of claim 130 wherein the polyolefincomposition further comprises an elastomer.
 139. The article of claim130 wherein the polyolefin composition further comprises a plastomer.140. The article of claim 130 where the one or more polypropylene impactcopolymers or polypropylene impact copolymer blends comprises apolypropylene polymer having an Mw of 30,000 to 1,000,000 g/mol. 141.The article of claim 130 where the one or more polypropylene impactcopolymers or polypropylene impact copolymer blends comprises apolypropylene polymer having an Mw/Mn of 1.6 to
 10. 142. The article ofclaim 130 where the one or more polypropylene impact copolymers orpolypropylene impact copolymer blends comprises a polypropylene polymerhaving a melting point (second melt) of 30 to 185° C.
 143. The articleof claim 130 where the one or more polypropylene impact copolymers orpolypropylene impact copolymer blends comprises a polypropylene polymerhaving a crystallinity of 5 to 80%.
 144. The article of claim 130 wherethe one or more polypropylene impact copolymers or polypropylene impactcopolymer blends comprises a polypropylene polymer having a heat offusion between 20 to 150 J/g.
 145. The article of claim 130 wherein thepolyolefin composition has a Gardner impact strength, tested on 0.125inch disk at 23° C. of 20 in-lb to 1000 in-lb.
 146. The article of claim130 wherein the polyolefin composition has a 1% secant flexural modulusof from 100 MPa to 2300 MPa.
 147. The article of claim 130 wherein thepolyolefin composition has a melt flow rate from 0.3 to 500 dg/min. 148.The article of claim 130 where the polyolefin comprises a copolymer ofpropylene and from 0.5 to 30 weight % of one or more comonomers selectedfrom the group consisting of ethylene, butene, pentene, hexene, heptene,octene, nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,5-ethyl-1-nonene, and 3,5,5-trimethyl-hexene-1.
 149. Thearticle of claim 130 where the polyolefin is present at 50 to 99.99weight %, based upon the weight of the polyolefin and thenon-functionalized plasticizer.
 150. The article of claim 130 wherenon-functionalized plasticizer is present at 0.5 to 35 weight %, basedupon the weight of the polyolefin and the non-functionalizedplasticizer.
 151. The article of claim 130, wherein the articlecomprises a molded article, packaging material, a package, a film, asheet, an extruded article, a thermoformed article, a blow moldedarticle, or an injection molded article.
 152. An article comprisingplasticized polyolefin composition comprising a polyolefin and anon-functionalized plasticizer where the plasticizer comprises a mixtureof branched and normal paraffins having from 6 to 50 carbon atoms and aratio of branch paraffin to n-paraffin ratio ranging from 0.5:1 to 9:1.153. The article of claim 152 where the mixture comprises greater than50 wt % mono-methyl species.
 154. The article of claim 152 where theplasticizer comprises a mixture of branched and normal paraffins havingfrom 10 to 16 carbon atoms and a ratio of branch paraffin to n-paraffinratio ranging from 1:1 to 4:1.